Hydrolysis-resistant silicone compounds

ABSTRACT

In one aspect, the invention relates to hydrolysis-resistant silicone compounds. In particular, disclosed are sterically hindered hydrolysis-resistant silicone compounds and improved purity hydrolysis-resistant silicone compounds. Also disclosed are processes for making hydrolysis-resistant silicone compounds; the products of the disclosed processes; compositions and polymers comprising the disclosed compounds and products of the disclosed processes; and ophthalmic lenses, for example contact lenses, intraocular lenses, artificial cornea, and spectacle lenses, comprising the disclosed compositions, disclosed polymers, disclosed compounds, and products of the disclosed processes. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present invention.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. Nonprovisional application Ser.No. 12/901,191, filed Oct. 8, 2010, which application claimed thebenefit of U.S. Nonprovisional application Ser. No. 11/561,456, filedNov. 20, 2006, which application claimed the benefit of U.S. ProvisionalApplication No. 60/848,317, filed Sep. 29, 2006, all of which are herebyincorporated herein by reference in their entireties.

BACKGROUND

As monomers for preparing ophthalmic lenses, monomers havingsilicon-containing groups are known. For example,3-[tris(trimethylsiloxy)silyl]propyl methacrylate is widely used as amonomer for preparing ophthalmic lenses. The polymer obtained bycopolymerizing 3-[tris(trimethylsiloxy)silyl]propyl methacrylate andN,N-dimethylacrylamide which is a hydrophilic monomer has advantageousfeatures that it is transparent and has a high oxygen permeability.However, if a carboxylic acid such as methacrylic acid is used as acopolymerization component in order to obtain a higher moisture content,the silicone component is gradually hydrolyzed, so that the physicalproperties of the contact lens may be degraded when the contact lens isstored for a long period.

On the other hand, to improve the hydrolysis resistance,3-[tris(triethylsiloxy)silyl]propyl methacrylate described in U.S. Pat.No. 3,377,371 was prepared, and hydrolysis test was conducted afteradding a carboxylic acid. As a result, although the polymer exhibited arelatively good stability at 80° C., it was proved that it is hydrolyzedat 90° C.

Thus, conventional silicon-containing materials typically fail toprovide satisfactory hydrolysis resistance while retaining advantageoustransparency and oxygen permeability. Therefore, there remains a needfor methods and compositions that overcome these deficiencies and thateffectively provide hydrolysis resistant silicon-containing materials.

SUMMARY

As embodied and broadly described herein, the invention, in one aspect,relates to hydrolysis-resistant silicone compounds.

Disclosed are sterically hindered hydrolysis-resistant siliconecompounds. For example, the compounds can have a sterically hinderedterminal silicon group. As a further example, the compounds can havecyclic siloxane moieties.

Also disclosed are improved purity hydrolysis-resistant siliconecompounds. For example, the compounds can be provided having lessdisiloxane side-product(s).

Also disclosed are processes for making hydrolysis-resistant siliconecompounds. In a further aspect, the invention relates to reacting analkoxysilyl compound with one or more silyl halide compounds. In a yetfurther aspect, the invention relates to reacting a silyl halide with asilanol. In a yet further aspect, the invention relates to preparingcyclic siloxane monomers.

Also disclosed are the products of the disclosed processes.

Also disclosed are compositions and polymers comprising the disclosedcompounds and products of the disclosed processes.

Also disclosed are ophthalmic lenses, for example contact lenses,intraocular lenses, artificial cornea, and spectacle lenses, comprisingthe disclosed compositions, disclosed polymers, disclosed compounds, andproducts of the disclosed processes.

Additional advantages of the invention will be set forth in part in thedescription which follows, and in part will be obvious from thedescription, or can be learned by practice of the invention. Theadvantages of the invention will be realized and attained by means ofthe elements and combinations particularly pointed out in the appendedclaims. It is to be understood that both the foregoing generaldescription and the following detailed description are exemplary andexplanatory only and are not restrictive of the invention, as claimed.

BRIEF DESCRIPTION OF THE FIGURES

The accompanying drawings, which are incorporated in and constitute apart of this specification, illustrate several embodiments and togetherwith the description illustrate the disclosed compositions and methods.

FIG. 1 shows a plot of R (1/Q) versus thickness (lm).

FIG. 2 shows an apparatus for oxygen permeability measurement.

FIG. 3 shows the structure of an electrode unit used to measure oxygenpermeability.

FIG. 4 shows a schematic of an oxygen permeability measurement setup.

DETAILED DESCRIPTION

The present invention can be understood more readily by reference to thefollowing detailed description of aspects of the invention and theExamples included therein.

Before the present compounds, compositions, articles, devices, and/ormethods are disclosed and described, it is to be understood that theyare not limited to specific synthetic methods unless otherwisespecified, or to particular reagents unless otherwise specified, as suchmay, of course, vary. It is also to be understood that the terminologyused herein is for the purpose of describing particular embodiments onlyand is not intended to be limiting. Although any methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of the present invention, example methods andmaterials are now described.

All publications mentioned herein are incorporated herein by referenceto disclose and describe the methods and/or materials in connection withwhich the publications are cited. The publications discussed herein areprovided solely for their disclosure prior to the filing date of thepresent application. Nothing herein is to be construed as an admissionthat the present invention is not entitled to antedate such publicationby virtue of prior invention. Further, the dates of publication providedherein can be different from the actual publication dates, which mayneed to be independently confirmed.

A. DEFINITIONS

As used in the specification and the appended claims, the singular forms“a,” “an” and “the” include plural referents unless the context clearlydictates otherwise. Thus, for example, reference to “a component,” “apolymer,” or “a residue” includes mixtures of two or more suchcomponents, polymers, or residues, and the like.

Ranges can be expressed herein as from “about” one particular value,and/or to “about” another particular value. When such a range isexpressed, another embodiment includes from the one particular valueand/or to the other particular value. Similarly, when values areexpressed as approximations, by use of the antecedent “about,” it willbe understood that the particular value forms another embodiment. Itwill be further understood that the endpoints of each of the ranges aresignificant both in relation to the other endpoint, and independently ofthe other endpoint. It is also understood that there are a number ofvalues disclosed herein, and that each value is also herein disclosed as“about” that particular value in addition to the value itself. Forexample, if the value “10” is disclosed, then “about 10” is alsodisclosed. It is also understood that each unit between two particularunits are also disclosed. For example, if 10 and 15 are disclosed, then11, 12, 13, and 14 are also disclosed.

A residue of a chemical species, as used in the specification andconcluding claims, refers to the moiety that is the resulting product ofthe chemical species in a particular reaction scheme or subsequentformulation or chemical product, regardless of whether the moiety isactually obtained from the chemical species. Thus, an ethylene glycolresidue in a polyester refers to one or more —OCH₂CH₂O— units in thepolyester, regardless of whether ethylene glycol was used to prepare thepolyester. Similarly, a sebacic acid residue in a polyester refers toone or more —CO(CH₂)₈CO— moieties in the polyester, regardless ofwhether the residue is obtained by reacting sebacic acid or an esterthereof to obtain the polyester.

As used herein, the terms “optional” or “optionally” means that thesubsequently described event or circumstance may or may not occur, andthat the description includes instances where said event or circumstanceoccurs and instances where it does not.

As used herein, the term “copolymer” refers to a polymer formed from twoor more different repeating units (monomer residues). By way of exampleand without limitation, a copolymer can be an alternating copolymer, arandom copolymer, a block copolymer, or a graft copolymer.

As used herein, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a broad aspect, thepermissible substituents include acyclic and cyclic, branched andunbranched, carbocyclic and heterocyclic, and aromatic and nonaromaticsubstituents of organic compounds. Illustrative substituents include,for example, those described below. The permissible substituents can beone or more and the same or different for appropriate organic compounds.For purposes of this disclosure, the heteroatoms, such as nitrogen, canhave hydrogen substituents and/or any permissible substituents oforganic compounds described herein which satisfy the valences of theheteroatoms. This disclosure is not intended to be limited in any mannerby the permissible substituents of organic compounds. Also, the terms“substitution” or “substituted with” include the implicit proviso thatsuch substitution is in accordance with permitted valence of thesubstituted atom and the substituent, and that the substitution resultsin a stable compound, e.g., a compound that does not spontaneouslyundergo transformation such as by rearrangement, cyclization,elimination, etc.

In defining various terms, “A¹,” “A²,” “A³,” and “A⁴” are used herein asgeneric symbols to represent various specific substituents. Thesesymbols can be any substituent, not limited to those disclosed herein,and when they are defined to be certain substituents in one instance,they can, in another instance, be defined as some other substituents.

The term “alkyl” as used herein is a branched or unbranched saturatedhydrocarbon group of 1 to 24 carbon atoms, for example, 1 to 12 carbonatoms, or 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl,s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl,tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkylgroup can also be substituted or unsubstituted. The alkyl group can besubstituted with one or more groups including, but not limited to,substituted or unsubstituted alkyl, cycloalkyl, alkoxy, amino, ether,halide, hydroxy, nitro, silyl, sulfo-oxo, or thiol, as described herein.A “lower alkyl” group is an alkyl group containing from one to sixcarbon atoms.

Throughout the specification “alkyl” is generally used to refer to bothunsubstituted alkyl groups and substituted alkyl groups; however,substituted alkyl groups are also specifically referred to herein byidentifying the specific substituent(s) on the alkyl group. For example,the term “halogenated alkyl” specifically refers to an alkyl group thatis substituted with one or more halide, e.g., fluorine, chlorine,bromine, or iodine. The term “alkoxyalkyl” specifically refers to analkyl group that is substituted with one or more alkoxy groups, asdescribed below. The term “alkylamino” specifically refers to an alkylgroup that is substituted with one or more amino groups, as describedbelow, and the like. When “alkyl” is used in one instance and a specificterm such as “alkylalcohol” is used in another, it is not meant to implythat the term “alkyl” does not also refer to specific terms such as“alkylalcohol” and the like.

This practice is also used for other groups described herein. That is,while a term such as “cycloalkyl” refers to both unsubstituted andsubstituted cycloalkyl moieties, the substituted moieties can, inaddition, be specifically identified herein; for example, a particularsubstituted cycloalkyl can be referred to as, e.g., an“alkylcycloalkyl.” Similarly, a substituted alkoxy can be specificallyreferred to as, e.g., a “halogenated alkoxy,” a particular substitutedalkenyl can be, e.g., an “alkenylalcohol,” and the like. Again, thepractice of using a general term, such as “cycloalkyl,” and a specificterm, such as “alkylcycloalkyl,” is not meant to imply that the generalterm does not also include the specific term.

The term “cycloalkyl” as used herein is a non-aromatic carbon-based ringcomposed of at least three carbon atoms. Examples of cycloalkyl groupsinclude, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, norbornyl, and the like. The term “heterocycloalkyl” is atype of cycloalkyl group as defined above, and is included within themeaning of the term “cycloalkyl,” where at least one of the carbon atomsof the ring is replaced with a heteroatom such as, but not limited to,nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl group andheterocycloalkyl group can be substituted or unsubstituted. Thecycloalkyl group and heterocycloalkyl group can be substituted with oneor more groups including, but not limited to, substituted orunsubstituted alkyl, cycloalkyl, alkoxy, amino, ether, halide, hydroxy,nitro, silyl, sulfo-oxo, or thiol as described herein.

The term “polyalkylene group” as used herein is a group having two ormore CH₂ groups linked to one another. The polyalkylene group can berepresented by the formula —(CH₂)_(a)—, where “a” is an integer of from2 to 500.

The terms “alkoxy” and “alkoxyl” as used herein to refer to an alkyl orcycloalkyl group bonded through an ether linkage; that is, an “alkoxy”group can be defined as —OA¹ where A¹ is alkyl or cycloalkyl as definedabove. “Alkoxy” also includes polymers of alkoxy groups as justdescribed; that is, an alkoxy can be a polyether such as —OA¹-OA² or—OA¹-(OA²)_(a)-OA³, where “a” is an integer of from 1 to 200 and A¹, A²,and A³ are alkyl and/or cycloalkyl groups.

The term “alkenyl” as used herein is a hydrocarbon group of from 2 to 24carbon atoms with a structural formula containing at least onecarbon-carbon double bond. Asymmetric structures such as (A¹A²)C═C(A³A⁴)are intended to include both the E and Z isomers. This can be presumedin structural formulae herein wherein an asymmetric alkene is present,or it can be explicitly indicated by the bond symbol C═C. The alkenylgroup can be substituted with one or more groups including, but notlimited to, substituted or unsubstituted alkyl, cycloalkyl, alkoxy,alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl,aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone,azide, nitro, silyl, sulfo-oxo, or thiol, as described herein.

The term “cycloalkenyl” as used herein is a non-aromatic carbon-basedring composed of at least three carbon atoms and containing at least onecarbon-carbon double bound, i.e., C═C. Examples of cycloalkenyl groupsinclude, but are not limited to, cyclopropenyl, cyclobutenyl,cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl,norbornenyl, and the like. The term “heterocycloalkenyl” is a type ofcycloalkenyl group as defined above, and is included within the meaningof the term “cycloalkenyl,” where at least one of the carbon atoms ofthe ring is replaced with a heteroatom such as, but not limited to,nitrogen, oxygen, sulfur, or phosphorus. The cycloalkenyl group andheterocycloalkenyl group can be substituted or unsubstituted. Thecycloalkenyl group and heterocycloalkenyl group can be substituted withone or more groups including, but not limited to, substituted orunsubstituted alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl,cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester,ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiolas described herein.

The term “alkynyl” as used herein is a hydrocarbon group of 2 to 24carbon atoms with a structural formula containing at least onecarbon-carbon triple bond. The alkynyl group can be unsubstituted orsubstituted with one or more groups including, but not limited to,substituted or unsubstituted alkyl, cycloalkyl, alkoxy, alkenyl,cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino,carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro,silyl, sulfo-oxo, or thiol, as described herein.

The term “cycloalkynyl” as used herein is a non-aromatic carbon-basedring composed of at least seven carbon atoms and containing at least onecarbon-carbon triple bound. Examples of cycloalkynyl groups include, butare not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and thelike. The term “heterocycloalkynyl” is a type of cycloalkenyl group asdefined above, and is included within the meaning of the term“cycloalkynyl,” where at least one of the carbon atoms of the ring isreplaced with a heteroatom such as, but not limited to, nitrogen,oxygen, sulfur, or phosphorus. The cycloalkynyl group andheterocycloalkynyl group can be substituted or unsubstituted. Thecycloalkynyl group and heterocycloalkynyl group can be substituted withone or more groups including, but not limited to, substituted orunsubstituted alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl,cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester,ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiolas described herein.

The term “aryl” as used herein is a group that contains any carbon-basedaromatic group including, but not limited to, benzene, naphthalene,phenyl, biphenyl, phenoxybenzene, and the like. The term “aryl” alsoincludes “heteroaryl,” which is defined as a group that contains anaromatic group that has at least one heteroatom incorporated within thering of the aromatic group. Examples of heteroatoms include, but are notlimited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term“non-heteroaryl,” which is also included in the term “aryl,” defines agroup that contains an aromatic group that does not contain aheteroatom. The aryl group can be substituted or unsubstituted. The arylgroup can be substituted with one or more groups including, but notlimited to, substituted or unsubstituted alkyl, cycloalkyl, alkoxy,alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl,aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone,azide, nitro, silyl, sulfo-oxo, or thiol as described herein. The term“biaryl” is a specific type of aryl group and is included in thedefinition of “aryl.” Biaryl refers to two aryl groups that are boundtogether via a fused ring structure, as in naphthalene, or are attachedvia one or more carbon-carbon bonds, as in biphenyl.

The term “aldehyde” as used herein is represented by the formula —C(O)H.Throughout this specification “C(O)” is a short hand notation for acarbonyl group, i.e., C═O.

The terms “amine” or “amino” as used herein are represented by theformula NA¹A²A³, where A¹, A², and A³ can be, independently, hydrogen orsubstituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl,alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.

The term “carboxylic acid” as used herein is represented by the formula—C(O)OH.

The term “ester” as used herein is represented by the formula —OC(O)A¹or —C(O)OA¹, where A¹ can be a substituted or unsubstituted alkyl,cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, orheteroaryl group as described herein. The term “polyester” as usedherein is represented by the formula -(A¹O(O)C-A²-C(O)O)_(a)— or-(A¹O(O)C-A²-OC(O))_(a)—, where A¹ and A² can be, independently, asubstituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl,alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein and“a” is an integer from 1 to 500. “Polyester” is as the term used todescribe a group that is produced by the reaction between a compoundhaving at least two carboxylic acid groups with a compound having atleast two hydroxyl groups.

The term “ether” as used herein is represented by the formula A¹OA²,where A¹ and A² can be, independently, a substituted or unsubstitutedalkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl,or heteroaryl group described herein. The term “polyether” as usedherein is represented by the formula -(A¹O-A²O)_(a)—, where A¹ and A²can be, independently, a substituted or unsubstituted alkyl, cycloalkyl,alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl groupdescribed herein and “a” is an integer of from 1 to 500. Examples ofpolyether groups include polyethylene oxide, polypropylene oxide, andpolybutylene oxide.

The term “halide” as used herein refers to the halogens fluorine,chlorine, bromine, and iodine.

The term “hydroxyl” as used herein is represented by the formula —OH.

The term “ketone” as used herein is represented by the formula A¹C(O)A²,where A¹ and A² can be, independently, a substituted or unsubstitutedalkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl,or heteroaryl group as described herein.

The term “azide” as used herein is represented by the formula —N₃.

The term “nitro” as used herein is represented by the formula —NO₂.

The term “nitrile” as used herein is represented by the formula —CN.

The term “silyl” as used herein is represented by the formula —SiA¹A²A³,where A¹, A², and A³ can be, independently, hydrogen or a substituted orunsubstituted alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl,cycloalkynyl, aryl, or heteroaryl group as described herein.

The term “sulfo-oxo” as used herein is represented by the formulas—S(O)A¹, —S(O)₂A¹, —OS(O)₂A¹, or —OS(O)₂OA¹, where A¹ can be hydrogen ora substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl,alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.Throughout this specification “S(O)” is a short hand notation for S═O.The term “sulfonyl” is used herein to refer to the sulfo-oxo grouprepresented by the formula —S(O)₂A¹, where A¹ can be hydrogen or asubstituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl,alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.The term “sulfone” as used herein is represented by the formulaA¹S(O)₂A², where A¹ and A² can be, independently, a substituted orunsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl,cycloalkynyl, aryl, or heteroaryl group as described herein. The term“sulfoxide” as used herein is represented by the formula A¹S(O)A², whereA¹ and A² can be, independently, a substituted or unsubstituted alkyl,cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, orheteroaryl group as described herein.

The term “thiol” as used herein is represented by the formula —SH.

As used herein, the term “siloxanyl” refers to a structure having atleast one Si—O—Si bond. Thus, for example, siloxanyl group means a grouphaving at least one Si—O—Si moiety, and siloxanyl compound means acompound having at least one Si—O—Si group.

As used herein, the term “alkoxysilyl” refers to a structure having atleast one Si—O-A¹ bond. Thus, for example, alkoxysilyl group means agroup having at least one Si—O-A¹ moiety, and alkoxysilyl compound meansa compound having at least one Si—O-A¹ group. In a further aspect,alkoxysilyl can have one Si—O-A¹ group. In various aspects, A¹ of analkoxysilyl moiety can be a substituted or unsubstituted alkyl,cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, orheteroaryl group as described herein. It is also contemplated that theterm alkoxysilyl can, in a further aspect, include substitutedalkoxysilyl groups and alkoxysilyl derivatives, including hydrolyzedalkoxysilyl groups (i.e., silanol groups).

As used herein, the term “silyl halide” refers to a structurerepresented by a formula X¹SiA¹A²A³ or X¹X²SiA¹A² or X¹X²X³SiA¹ orX¹X²X³X⁴Si, where X¹, X², X³, and X⁴ are independently fluorine,chlorine, bromine, or iodine, and where A¹, A², and A³ are,independently, hydrogen or a substituted or unsubstituted alkyl,cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl,or heteroaryl group as described herein. In a further aspect, silylhalide can have the structure X¹SiA¹A²A³.

As used herein, the term “silanol” refers to a silyl moiety having astructure represented by the formula —SiA¹A²A³A⁴, where A¹, A², A³, andA⁴ can be, independently, hydrogen or a substituted or unsubstitutedalkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl,aryl, or heteroaryl group as described herein, with the proviso that atleast one of A¹, A², A³, and A⁴ is hydroxyl. In a further aspect, one ofA¹, A², A³, and A⁴ is hydroxyl.

As used herein, the terms “silanoxy” and “silanoxyl” refer to a silylmoiety having a structure represented by the formula —OSiA¹A²A³, whereA¹, A², and A³ can be, independently, hydrogen or a substituted orunsubstituted alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl,cycloalkynyl, aryl, or heteroaryl group as described herein.

As used herein, the term “alkylacrylic acid” refers to acrylic acid,alkyl-substituted acrylic acids, salts thereof, and derivatives thereof.In one aspect, an alkylacrylic acid can be further substituted. In afurther aspect, an alkylacrylic acid is methacrylic acid.

As used herein, the term “hydrolyzable group” refers to a group ormoiety which is convertible to hydrogen by hydrolysis or solvolysis. Inone aspect, a hydrolyzable group can be hydrolyzed (i.e., converted to ahydrogen group) by exposure to water or a protic solvent at or nearambient temperature and at or near atmospheric pressure. In furtheraspects, a hydrolyzable group can be hydrolyzed by exposure to water ora protic solvent at an elevated temperature or an elevated pressure. Infurther aspects, a hydrolyzable group can be hydrolyzed by exposure toacidic or alkaline water or acidic or alkaline protic solvent.

As used herein, the term “sterically hindered” refers to a tertiary orquaternary substituted moiety wherein at least one of the substituentshas at least two carbon atoms. For example, a sterically hindered moietycan have the structure:

wherein A¹ is a carbon atom or silicon atom and wherein at least one ofA², A³, and A⁴ is an organic group having at least two carbon atoms. Ina further aspect, at least one of A², A³, and A⁴ is methyl, and at leastone of A², A³, and A⁴ is an organic group having at least two carbonatoms.

One example of a sterically hindered group is a sterically hinderedterminal silicon group, which can have the structure:

wherein at least one of A², A³, and A⁴ is an organic group having atleast two carbon atoms. In a further aspect, at least one of A², A³, andA⁴ is methyl, and at least one of A², A³, and A⁴ is an organic grouphaving at least two carbon atoms.

As used herein, the term “radical-polymerizable group” refers to amoiety that can undergo addition polymerization when exposed to aradical source, for example a radical initiator. Radical polymerizablegroups include olefins and acrylates, for example acrylic acid and itsderivatives (e.g., alkyl acrylates) and methacrylic acid and itsderivatives (e.g., alkyl methacrylates). Such a polymerization typicallyproceeds through a chain growth mechanism and exhibits chain growthkinetics.

As used herein, the term “hydrolysis resistance” refers to the capacityof a compound or composition to survive hydrolysis conditions. In oneaspect, acid hydrolysis is contemplated. As used herein, the term“hydrolysis-resistant” refers to the characteristic of survivinghydrolysis conditions. In one aspect, a residue of a compound can bereferred to as hydrolysis-resistant if a composition exhibits greaterhydrolysis resistance when comprising the residue of the compound ascompared to a similar composition in the absence of the residue of thecompound.

Unless stated to the contrary, a formula with chemical bonds shown onlyas solid lines and not as wedges or dashed lines contemplates eachpossible isomer, e.g., each enantiomer and diastereomer, and a mixtureof isomers, such as a racemic or scalemic mixture.

Disclosed are the components to be used to prepare the compositions ofthe invention as well as the compositions themselves to be used withinthe methods disclosed herein. These and other materials are disclosedherein, and it is understood that when combinations, subsets,interactions, groups, etc. of these materials are disclosed that whilespecific reference of each various individual and collectivecombinations and permutation of these compounds may not be explicitlydisclosed, each is specifically contemplated and described herein. Forexample, if a particular compound is disclosed and discussed and anumber of modifications that can be made to a number of moleculesincluding the compounds are discussed, specifically contemplated is eachand every combination and permutation of the compound and themodifications that are possible unless specifically indicated to thecontrary. Thus, if a class of molecules A, B, and C are disclosed aswell as a class of molecules D, E, and F and an example of a combinationmolecule, A-D is disclosed, then even if each is not individuallyrecited each is individually and collectively contemplated meaningcombinations, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C—F are considereddisclosed. Likewise, any subset or combination of these is alsodisclosed. Thus, for example, the sub-group of A-E, B-F, and C-E wouldbe considered disclosed. This concept applies to all aspects of thisapplication including, but not limited to, steps in methods of makingand using the compositions of the invention. Thus, if there are avariety of additional steps that can be performed it is understood thateach of these additional steps can be performed with any specificembodiment or combination of embodiments of the methods of theinvention.

It is understood that the compositions disclosed herein have certainfunctions. Disclosed herein are certain structural requirements forperforming the disclosed functions, and it is understood that there area variety of structures that can perform the same function that arerelated to the disclosed structures, and that these structures willtypically achieve the same result.

B. HYDROLYSIS-RESISTANT SILICONE COMPOUNDS

In one aspect, the invention relates to sterically hinderedhydrolysis-resistant silicone compounds. That is, a silicone compoundcan have at least one sterically hindered terminal silicon group and,thus, having improved resistance to hydrolysis conditions. In a furtheraspect, the invention relates to improved purity hydrolysis-resistantsilicone compounds. That is, a silicone compound can have decreaseddisiloxane side-product and, thus, improved yield and purity.

1. Sterically Hindered Hydrolysis-Resistant Silicone Compounds

In one aspect, the invention relates to sterically hinderedhydrolysis-resistant silicone compounds having the structure:

wherein M represents a radical-polymerizable group; wherein L representsan optionally substituted divalent C₁-C₂₀ organic group; wherein Z¹ toZ¹¹ independently represent optionally substituted C₁-C₂₀ alkyl groupsor optionally substituted C₆-C₂₀ aryl groups, with the provisos that: atleast one of Z³, Z⁴, and Z⁹ is methyl, and at least one of Z³, Z⁴, andZ⁹ is an organic group having at least two carbon atoms, at least one ofZ⁵, Z⁶, and Z¹⁰ is methyl, and at least one of Z⁵, Z⁶, and Z¹⁰ is anorganic group having at least two carbon atoms, and at least one of Z⁷,Z⁸, and Z¹¹ is methyl, and at least one of Z⁵, Z⁶, and Z¹⁰ is an organicgroup having at least two carbon atoms; wherein n represents an integerof from 0 to 200; and wherein a, b, and c independently representintegers of from 0 to 20, with the proviso that a, b, and c are notsimultaneously 0.

In one aspect, a, b, and c are 1. In a further aspect, n is 0. In afurther aspect, n is 0, and all of a, b, and c are 1. In a yet furtheraspect, a is 0; b and c are 1; and Z⁹ comprises a methyl group, an ethylgroup, a propyl group, a butyl group, or a phenyl group. In a stillfurther aspect, k is 0, and m is from 1 to 3. In an even further aspect,m is 2 or 3, and a, b, and c are independently from 1 to 20, forexample, from 1 to 16, from 1 to 12, from 1 to 8, from 1 to 6, from 1 to4, from 2 to 16, from 2 to 12, from 2 to 8, from 2 to 6, from 2 to 4, orfrom 4 to 20. In a further aspect, m is 2 or 3; a, b, and c are 1; and nis 0.

For example, a compound can have the structure:

wherein M represents a radical-polymerizable group; wherein L has thestructure:

wherein G is hydrogen or a hydrolyzable group; wherein k represents aninteger of 0 to 6, and wherein m represents an integer of 1 to 3 when kis 0, and represents an integer of 1 to 20 when k is not 0, with theproviso that 1<3k+m<20; wherein Z¹ to Z¹¹ independently representoptionally substituted C₁-C₂₀ alkyl groups or C₆-C₂₀ aryl groups, withthe provisos that: at least one of Z³, Z⁴, and Z⁹ is methyl, and atleast one of Z³, Z⁴, and Z⁹ is an organic group having at least twocarbon atoms, at least one of Z⁵, Z⁶, and Z¹⁰ is methyl, and at leastone of Z⁵, Z⁶, and Z¹⁰ is an organic group having at least two carbonatoms, and at least one of Z⁷, Z⁸, and Z¹¹ is methyl, and at least oneof Z⁵, Z⁶, and Z¹⁰ is an organic group having at least two carbon atoms;wherein n represents an integer of from 0 to 200; wherein a, b, and cindependently represent integers of from 0 to 20, with the proviso thata, b, and c are not simultaneously 0; and wherein the compound exhibitsa hydrolysis resistance of at least about 90% at about 90° C.

In one aspect, the sterically hindered hydrolysis-resistant siliconecompounds can be cyclic siloxane monomers and can have the structure:

wherein p is 1, 2, or 3; wherein M represents a radical-polymerizablegroup; wherein L represents an optionally substituted divalent C₁-C₂₀organic group; and wherein R¹, R^(2a), R^(2b), R^(3a), R^(3b), R^(4a),and R^(4b) independently represent optionally substituted C₁-C₂₀ alkylgroups or optionally substituted C₆-C₂₀ aryl groups.

a. Radical-Polymerizable Groups

In one aspect, the sterically hindered hydrolysis-resistant siliconecompounds of the invention bear at least one radical-polymerizablegroup, M. In one aspect, M is any moiety known to those of skill in theart that can undergo addition polymerization when exposed to a radicalsource, for example a radical initiator. In a further aspect, M can bean olefin. For example, M can be an alkene group, including an ethylene,a 1,3-butadiene moiety, or a styryl moiety. In a further aspect, M canbe an acrylate. For example, M can be a residue of acrylic acid or aderivative thereof (e.g., alkyl acrylates) or residue of methacrylicacid or a derivative thereof (e.g., alkyl methacrylates). Specifically,in one aspect, M can be an acryloyloxy group or a methacryloyloxy group.

In a further aspect, M can be an acryloyloxy group, a methacryloyloxygroup, acrylamide group, methacrylamide group, N-vinylamide group, orstyryl group.

It is understood that one radical-polymerizable group can undergo apolymerization reaction with other radical-polymerizable groups of othercompounds of the invention or with radical-polymerizable groups ofcomonomers, thereby producing a polymer comprising a residue of acompound of the invention.

b. Linking Groups

In one aspect, the sterically hindered hydrolysis-resistant siliconecompounds of the invention optionally bear at least one linking group,L. In one aspect, L can be an optionally substituted divalent C₁-C₂₀organic group, for example, a substituted or unsubstituted C₁-C₁₆organic group, C₁-C₁₂ organic group, C₁-C₈ organic group, or a C₁-C₄organic group. In a further aspect, linking group, L, can be asubstituted or unsubstituted polyalkylene group. That is, L can be agroup having two or more CH₂ groups linked to one another, representedby the formula —(CH₂)_(a)—, where “a” is an integer of from 1 to 20.Examples include methylene, ethylene, propylene, butylene, pentylene,and hexylene. The organic group can be branched or linear.

In a further aspect, linking group, L, can be substituted by one or morefunctionalized groups. For example, L can be substituted by hydroxygroups, hydroxyalkyl groups, amino groups, aminoalkyl groups, amidegroups, alkylamide groups, alkoxy groups, alkoxyalkyl groups,alkoxycarbonyl groups, alkoxycabonylalkyl groups or a combination ofthose functionalized groups. In a yet further aspect, L can besubstituted by hydroxy groups or hydroxyalkyl groups. Specifically, inone aspect, L can be substituted by hydroxy groups.

In a further aspect, one or more CH₂ groups of linking group, L, can bereplaced by one or more hetero atoms. For example, one or more CH₂groups of L can be replaced by O, S, N—R^(L), P—R^(L) or a combinationof those hetero atoms, wherein R^(L) is substituted or unsubstitutedC₁-C₂₀ alkyl groups or substituted or unsubstituted C₆-C₂₀ aryl groupsand R^(L) can be substituted by one or more functionalized groups andCH₂ groups of R^(L) can be replaced by one or more hetero atoms. In ayet further aspect, one or more CH₂ groups of L can be replaced by O orN—R^(L).

In a further aspect, L has the structure:

wherein G is hydrogen or a hydrolyzable group; wherein k represents aninteger of 0 to 6; and wherein m represents an integer of 1 to 3 when kis 0, and represents an integer of from 1 to 20 when k is not 0, withthe proviso that 1<3k+m<20.

In a further aspect, k is 1, and wherein m is from 1 to 7. In a yetfurther aspect, L is absent from the compounds and/or compositions ofthe invention.

c. Siloxanyl Chains

In one aspect, the sterically hindered hydrolysis-resistant siliconecompounds of the invention can optionally bear siloxanyl chains having ageneral structure:

wherein Z¹ and Z² are, independently, substituted or unsubstitutedC₁-C₂₀ alkyl groups or substituted or unsubstituted C₆-C₂₀ aryl groups.

The C₁-C₂₀ alkyl groups can be, for example, C₁-C₁₆ alkyl groups, C₁-C₁₂alkyl groups, C₁-C₈ alkyl groups, C₁-C₆ alkyl groups, or C₁-C₄ alkylgroups. Examples include methyl, ethyl, n-propyl, i-propyl, n-butyl,s-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, neopentyl,hexyl, heptyl, octyl, decyl, and dodecyl. The alkyl groups can bebranched or linear.

The C₆-C₂₀ aryl groups can be, for example, C₆-C₂₀ aryl groups, C₆-C₁₂aryl groups, or C₆-C₁₀ aryl groups. Examples include phenyl, toluenyl,pyridinyl, and naphthalenyl.

n can be from 0 to 200, for example, from 0 to 100, from 0 to 50, from 0to 25, from 0 to 12, from 0 to 10, from 0 to 6, from 0 to 4, from 1 to200, from 1 to 100, from 1 to 50, from 1 to 25, from 1 to 12, from 1 to10, from 1 to 6, or from 1 to 4. It is understood that, in a polymer,the average for n can be a non-integer.

In a further aspect, the compounds of the invention can optionally bearsiloxanyl chains having a general structure:

wherein Z³ to Z¹¹ independently represent optionally substituted C₁-C₂₀alkyl groups or optionally substituted C₆-C₂₀ aryl groups, with theprovisos that: at least one of Z³, Z⁴, and Z⁹ is methyl, and at leastone of Z³, Z⁴, and Z⁹ is an organic group having at least two carbonatoms, at least one of Z⁵, Z⁶, and Z¹⁰ is methyl, and at least one ofZ⁵, Z⁶, and Z¹⁰ is an organic group having at least two carbon atoms,and at least one of Z⁷, Z⁸, and Z¹¹ is methyl, and at least one of Z⁵,Z⁶, and Z¹⁰ is an organic group having at least two carbon atoms.

The C₁-C₂₀ alkyl groups can be, for example, C₁-C₁₆ alkyl groups, C₁-C₁₂alkyl groups, C₁-C₈ alkyl groups, C₁-C₆ alkyl groups, or C₁-C₄ alkylgroups. Examples include methyl, ethyl, n-propyl, i-propyl, n-butyl,s-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, neopentyl,hexyl, heptyl, octyl, decyl, and dodecyl. The alkyl groups can bebranched or linear.

For example, each siloxanyl chain can, independently, have a structurerepresented by the formula:

The C₆-C₂₀ aryl groups can be, for example, C₆-C₂₀ aryl groups, C₆-C₁₂aryl groups, or C₆-C₁₀ aryl groups. Examples include phenyl, toluenyl,pyridinyl, and naphthalenyl.

For example, each siloxanyl chain can, independently, have a structurerepresented by the formula:

In a further aspect, each of a, b, and c can be an integers of from 0 to20, for example, from 0 to 12, from 0 to 10, from 0 to 8, from 0 to 6,from 0 to 4, from 1 to 20, from 0 to 12, from 0 to 10, from 0 to 8, from0 to 6, from 0 to 4, or from 1 to 20, including 1, 2, 3, 4, 5, 6, 7, 8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20. It is understoodthat, in a polymer, the average for any of a, b, and c can be anon-integer. Each of a, b, and c can be the same as or different fromthe others of a, b, and c.

In a further aspect, two of Z³, Z⁴, and Z⁹ are methyl, and one of Z³,Z⁴, and Z⁹ is ethyl, propyl, or butyl; wherein two of Z⁵, Z⁶, and Z¹⁰are methyl, and one of Z⁵, Z⁶, and Z¹⁰ is ethyl, propyl, or butyl; andtwo of Z⁷, Z⁸, and Z¹¹ are methyl, and one of Z⁵, Z⁶, and Z¹⁰ is ethyl,propyl, or butyl. In a yet further aspect, Z³, Z⁴, Z⁵, Z⁶, Z⁷, and Z⁸are methyl, and wherein and Z⁹, Z¹⁰, and Z¹¹ are independently ethyl,propyl, or butyl.

d. Illustrative Structures

As examples, the sterically hindered hydrolysis-resistant siliconecompounds of the invention can have a structure represented by theformula:

2. Improved Purity Hydrolysis-Resistant Silicone Compounds

In one aspect, the invention relates to improved purityhydrolysis-resistant silicone compounds having the structure:

wherein M represents a radical-polymerizable group; wherein L representsan optionally substituted divalent C₁-C₂₀ organic group; wherein R, R¹,R², and R³ independently represent optionally substituted C₁-C₂₀ alkylgroups or optionally substituted C₆-C₂₀ aryl groups, with the provisothat at least one of R¹, R², and R³ is a group having at least 2 carbonatoms; and wherein n represents an integer of from 1 to 3. In certainaspects, n is 1, n is 2, and n is 3.

Such improved purity hydrolysis-resistant silicone compounds compoundcan be prepared, for example, by the step of reacting a silyl halidehaving the structure:

wherein X represents a halogen selected from the group consisting ofchlorine, bromine, and iodine, with a silanol having the structure:

In a further aspect, such a compound can be produced in a yield of atleast about 10% by gas chromatography analysis. For example, the yieldcan be at least about 15%, at least about 20%, at least about 25%, atleast about 30%, at least about 35%, at least about 40%, at least about45%, or at least about 50% by gas chromatography analysis.

In a further aspect, k is 0, and m is from 1 to 3. In a yet furtheraspect, k is 1, and m is from 1 to 7. In a still further aspect, one ofR¹, R², and R³ is methyl, and at least one of R¹, R², and R³ is ethyl,propyl, or butyl. In an even further aspect, two of R¹, R², and R³ aremethyl, and one of R¹, R², and R³ is ethyl, propyl, or butyl.

In one aspect, water is substantially absent.

a. Radical-Polymerizable Groups

In one aspect, the improved purity hydrolysis-resistant siliconecompounds of the invention bear at least one radical-polymerizablegroup, M, as disclosed herein. It is also understood that oneradical-polymerizable group can undergo a polymerization reaction withother radical-polymerizable groups of other compounds of the inventionor with radical-polymerizable groups of comonomers, thereby producing apolymer comprising a residue of a compound of the invention.

b. Linking Groups

In one aspect, the improved purity hydrolysis-resistant siliconecompounds of the invention optionally bear at least one linking group,L, as disclosed herein. In a further aspect, L has the structure:

wherein k represents an integer of from 0 to 6; and wherein m representsan integer of from 1 to 3 when k is 0, and represents an integer of from1 to 20 when k is not 0, with the proviso that 1≦3k+m≦20. In a furtheraspect, k is 1, and wherein m is from 1 to 7. In a yet further aspect, Lis absent from the compounds and/or compositions of the invention.

c. Silanoxy Groups

In one aspect, the compounds of the invention can bear one, two, orthree silanoxy groups having a general structure:

wherein R, R¹, R², and R³ independently represent substituted orunsubstituted C₁-C₂₀ alkyl groups or substituted or unsubstituted C₆-C₂₀aryl groups.

The C₁-C₂₀ alkyl groups can be, for example, C₁-C₁₆ alkyl groups, C₁-C₁₂alkyl groups, C₁-C₈ alkyl groups, C₁-C₆ alkyl groups, or C₁-C₄ alkylgroups. Examples include methyl, ethyl, n-propyl, i-propyl, n-butyl,s-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, neopentyl,hexyl, heptyl, octyl, decyl, and dodecyl. The alkyl groups can bebranched or linear.

The C₆-C₂₀ aryl groups can be, for example, C₆-C₂₀ aryl groups, C₆-C₁₂aryl groups, or C₆-C₁₀ aryl groups. Examples include phenyl, toluenyl,pyridinyl, and naphthalenyl.

In a further aspect, at least one of R¹, R², and R³ is a group having atleast 2 carbon atoms. For example, each silanoxy group can,independently, have a structure represented by the formula:

d. Disiloxane Side-Product

In one aspect, a disiloxane compound having the structure:

is present in an amount of from about 0% to about 20% by gaschromatography analysis. For example, a disiloxane can be present in anamount of from about 0% to about 15%, from about 0% to about 10%, fromabout 0% to about 5%, from about 0% to about 3%, from about 0% to about3%, from about 0% to about 1%, or about 0% by gas chromatographyanalysis. In one aspect, a disiloxane compound is substantially absent.

C. PROCESSES FOR MAKING HYDROLYSIS-RESISTANT SILICONE COMPOUNDS

In one aspect, the invention relates processes for making stericallyhindered hydrolysis-resistant silicone compounds. That is, the processescan make a silicone compound having at least one sterically hinderedterminal silicon group and, thus, having improved resistance tohydrolysis conditions. In a further aspect, the invention relates toprocesses for making improved purity hydrolysis-resistant siliconecompounds. That is, the processes can make a silicone compound havingdecreased disiloxane side-product and, thus, improved yield and purity.

1. Reaction of Alkoxysilyl Compound with Silyl Halide Compound

In one aspect, the invention relates to a process for making ahydrolysis-resistant silicone compound having a sterically-hinderedterminal silicon group, the process comprising the step of reacting analkoxysilyl compound having the structure:

with one or more silyl halide compounds having the structure:

wherein X¹, X², and X³ independently represent a halogen selected fromthe group consisting of chlorine, bromine, and iodine; wherein Mrepresents a radical-polymerizable group; wherein L represents anoptionally substituted divalent C₁-C₂₀ organic group; wherein nrepresents an integer of from 0 to 200; wherein Q¹, Q², and Q³independently represent hydrogen or a hydrolyzable group; wherein Z¹ toZ¹¹ independently represent optionally substituted C₁-C₂₀ alkyl groupsor optionally substituted C₆-C₂₀ aryl groups, with the provisos that: atleast one of Z³, Z⁴, and Z⁹ is methyl, and at least one of Z³, Z⁴, andZ⁹ is an organic group having at least two carbon atoms, at least one ofZ⁵, Z⁶, and Z¹⁰ is methyl, and at least one of Z⁵, Z⁶, and Z¹⁰ is anorganic group having at least two carbon atoms, and at least one of Z⁷,Z⁸, and Z¹¹ is methyl, and at least one of Z⁵, Z⁶, and Z¹⁰ is an organicgroup having at least two carbon atoms; wherein a, a′, b, b′, c, and c′independently represent integers of from 0 to 20; and wherein (a+a′),(b+b′), and (c+c′) are, independently, integers of from 0 to 20, withthe proviso that (a+a′), (b+b′), and (c+c′) are not simultaneously 0.

In a further aspect, a, a′, b, b′, c, and c′ independently representintegers of from 0 to 20, for example, from 0 to 12, from 0 to 10, from0 to 8, from 0 to 6, from 0 to 4, from 1 to 20, from 0 to 12, from 0 to10, from 0 to 8, from 0 to 6, from 0 to 4, or from 1 to 20. Each of a,a′, b, b′, c, and c′ can be the same as or different from the others ofa, a′, b, b′, c, and c′. In a yet further aspect, (a+a′), (b+b′), and(c+c′) are, independently, integers of from 0 to 20, with the provisothat (a+a′), (b+b′), and (c+c′) are not simultaneously 0. For example,each of (a+a′), (b+b′), and (c+c′) can be, independently, an integer offrom 0 to 12, from 0 to 10, from 0 to 8, from 0 to 6, from 0 to 4, from1 to 20, from 0 to 12, from 0 to 10, from 0 to 8, from 0 to 6, from 0 to4, or from 1 to 20, including 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13,14, 15, 16, 17, 18, 19, and 20. It is understood that, in a polymer, theaverage for any of a, a′, b, b′, c, c′, (a+a′), (b+b′), and (c+c′) canbe a non-integer.

In a further aspect, Q¹, Q², and Q³ independently represent alkyl.

a. Radical-Polymerizable Groups

In one aspect, the processes of the invention produce compounds bearingat least one radical-polymerizable group, M, as disclosed herein. It isunderstood that a one radical-polymerizable group can undergo apolymerization reaction with other radical-polymerizable groups of othercompounds of the invention or with radical-polymerizable groups ofcomonomers, thereby producing a polymer comprising a residue of acompound of the invention.

b. Linking Groups

In one aspect, the processes of the invention produce compounds bearingat least one linking group, L, as disclosed herein. In a further aspect,linking group, L, can be substituted by one or more functionalizedgroups. For example, L can be substituted by hydroxy groups,hydroxyalkyl groups, amino groups, aminoalkyl groups, amide groups,alkylamide groups, alkoxy groups, alkoxyalkyl groups, alkoxycarbonylgroups, alkoxycabonylalkyl groups or a combination of thosefunctionalized groups. In a yet further aspect, L can be substituted byhydroxy groups or hydroxyalkyl groups. Specifically, in one aspect, Lcan be substituted by hydroxy groups.

In a further aspect, one or more CH₂ groups of linking group, L, can bereplaced by one or more hetero atoms. For example, one or more CH₂groups of L can be replaced by O, S, N—R^(L), P—R^(L) or a combinationof those hetero atoms, wherein R^(L) is substituted or unsubstitutedC₁-C₂₀ alkyl groups or substituted or unsubstituted C₆-C₂₀ aryl groupsand R^(L) can be substituted by one or more functionalized groups andCH₂ groups of R^(L) can be replaced by one or more hetero atoms. In ayet further aspect, one or more CH₂ groups of L can be replaced by O orN—R^(L).

In a further aspect, L has the structure:

wherein G is hydrogen or a hydrolyzable group; wherein k represents aninteger of 0 to 6; and wherein m represents an integer of 1 to 3 when kis 0, and represents an integer of from 1 to 20 when k is not 0, withthe proviso that 1<3k+m<20.

In a further aspect, k is 1, and wherein m is from 1 to 7. In a yetfurther aspect, L is absent from the processes of the invention.

c. Siloxanyl Chains

In one aspect, the processes of the invention produce compoundsoptionally bearing siloxanyl chains having a general structure:

as disclosed herein.

d. Alkoxysilyl Compound

In one aspect, the processes of the invention relate to an alkoxysilylcompound having the structure:

In a further aspect, Q¹, Q², and Q³ independently represent hydrogen ora hydrolyzable group. For example, Q¹, Q², and Q³ can independentlyrepresent an alkyl or aryl group including a methyl group, an ethylgroup, a propyl group, a butyl group, a benzyl group, or a benzoylgroup.

In a further aspect, Z¹ to Z⁸ independently represent optionallysubstituted C₁-C₂₀ alkyl groups or optionally substituted C₆-C₂₀ arylgroups. The C₁-C₂₀ alkyl groups can be, for example, C₁-C₁₆ alkylgroups, C₁-C₁₂ alkyl groups, C₁-C₈ alkyl groups, C₁-C₆ alkyl groups, orC₁-C₄ alkyl groups. Examples include methyl, ethyl, n-propyl, i-propyl,n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl,neopentyl, hexyl, heptyl, octyl, decyl, and dodecyl. The alkyl groupscan be branched or linear. The C₆-C₂₀ aryl groups can be, for example,C₆-C₂₀ aryl groups, C₆-C₁₂ aryl groups, or C₆-C₁₀ aryl groups. Examplesinclude phenyl, toluenyl, pyridinyl, and naphthalenyl.

n can be from 0 to 200, for example, from 0 to 100, from 0 to 50, from 0to 25, from 0 to 12, from 0 to 10, from 0 to 6, from 0 to 4, from 1 to200, from 1 to 100, from 1 to 50, from 1 to 25, from 1 to 12, from 1 to10, from 1 to 6, or from 1 to 4. It is understood that, in a polymer,the average for n can be a non-integer.

In a further aspect, a, b, and c independently represent integers offrom 0 to 20, for example, from 0 to 12, from 0 to 10, from 0 to 8, from0 to 6, from 0 to 4, from 1 to 20, from 0 to 12, from 0 to 10, from 0 to8, from 0 to 6, from 0 to 4, or from 1 to 20, including 1, 2, 3, 4, 5,6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20. Each of a,b, and c can be the same as or different from the others of a, b, and c.It is understood that, in a polymer, the average for any of a, b, and ccan be a non-integer.

In a yet further aspect, the alkoxysilyl compound can have thestructure:

e. Silyl Halide Compound

In one aspect, silyl halides suitable for use in the process of thepresent invention have the structure:

In one aspect, X¹, X², and X³ independently represent a halogen selectedfrom the group consisting of chlorine, bromine, and iodine.

In a further aspect, Z³ to Z¹¹ independently represent optionallysubstituted C₁-C₂₀ alkyl groups or optionally substituted C₆-C₂₀ arylgroups. The C₁-C₂₀ alkyl groups can be, for example, C₁-C₁₆ alkylgroups, C₁-C₁₂ alkyl groups, C₁-C₈ alkyl groups, C₁-C₆ alkyl groups, orC₁-C₄ alkyl groups. Examples include methyl, ethyl, n-propyl, i-propyl,n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl,neopentyl, hexyl, heptyl, octyl, decyl, and dodecyl. The alkyl groupscan be branched or linear. The C₆-C₂₀ aryl groups can be, for example,C₆-C₂₀ aryl groups, C₆-C₁₂ aryl groups, or C₆-C₁₀ aryl groups. Examplesinclude phenyl, toluenyl, pyridinyl, and naphthalenyl.

In a further aspect, a′, b′, and c′ independently represent integers offrom 0 to 20, for example, from 0 to 12, from 0 to 10, from 0 to 8, from0 to 6, from 0 to 4, from 1 to 20, from 0 to 12, from 0 to 10, from 0 to8, from 0 to 6, from 0 to 4, or from 1 to 20, including 1, 2, 3, 4, 5,6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20. Each of a′,b′, and c′ can be the same as or different from the others of a′, b′,and c′. It is understood that, in a polymer, the average for any of a′,b′, and c′ can be a non-integer.

In a further aspect, a silyl halide compound has the structure:

f. Reaction Conditions

Typically, an alkoxysilyl compound (e.g., trialkoxysilylalkylacrylate)and at least about three molar equivalents of a silyl halide (e.g.,trialkylsilyl halide) are added to a mixture of water, alcohol, and anorganic solvent. The trialkoxysilylalkylacrylate and the trialkylsilylhalide can be added separately or as a mixture and are typically addedby way of dropping funnel. Such addition is typically performed whilethe mixture is agitated by, for example, stirring, shaking, orsonicating.

i. Reagents

In one aspect, an alkoxysilyl compound as disclosed herein, for examplea trialkoxysilylalkylacrylate, can be used in connection with thedisclosed methods. Typically, one molar equivalent of this reagent isused.

In one aspect, a silyl halide as disclosed herein, for example atrialkylsilyl halide, can be used in connection with the disclosedmethods. Although one of ordinary skill in the art of organic synthesiscan readily determine the relative amount of silyl halide to be used ina reaction, typically, at least three molar equivalents of the silylhalide, relative to the alkoxysilyl compound, are used. In a furtheraspect, when an excess is desired, four, five, six, or more molarequivalents can be used.

In one aspect, water can be used in connection with the disclosedmethods. More specifically, water can be used in the mixture to whichthe alkoxysilyl compound and the silyl halide are added. In furtheraspects, the water is deionized water or distilled water. Typically,about 0.5 mL of water is used per 1 mmol of alkoxysilyl compound to bereacted; however, from about 0.1 mL to about 3.0 mL of water can be usedper 1 mmol of alkoxysilyl compound. Without wishing to be bound bytheory, it is believed that the water participates in hydrolysis of thealkoxysilyl compound, thereby forming a nucleophile, which then reactswith the silyl halide.

In one aspect, an alcohol can be used in connection with the disclosedmethods. The alcohol can be, for example, methanol, ethanol, n-propanol,i-propanol, n-butanol, i-butanol, s-butanol, t-butanol, pentanol,hexanol, or other C₇-C₁₂ alcohol. In a further aspect, the alcohol ismiscible with water. Typically, about 0.5 mL of alcohol is used per 1 mLof water in the mixture; however, from about 0.1 mL to about 3.0 mL ofalcohol can be used per 1 mL of water.

In one aspect, an organic solvent can be used in connection with thedisclosed methods. In various aspects, the organic solvent can be ahydrocarbon, including pentane, cyclopentane, hexane, cyclohexane,heptane, octane, nonane, or decane; an ether, including diethyl ether;or an amide, including dimethylformamide, dimethylformamide,dimethylacetamide, and diethylacetamide. In a further aspect, theorganic solvent is selected so as to be immiscible with water.Typically, about 0.5 mL of organic solvent is used per 1 mL of water inthe mixture; however, from about 0.1 mL to about 3.0 mL of organicsolvent can be used per 1 mL of water.

ii. Temperature and Pressure

The addition is typically carried out at a temperature of from about 0°C. to about 10° C., for example, from about 0° C. to about 5° C. or fromabout 2° C. to about 3° C. That is, the mixture of water, alcohol, andan organic solvent is typically cooled before and/or during addition ofthe alkoxysilyl compound and the silyl halide. In a further aspect, thealkoxysilyl compound and/or the silyl halide are cooled before and/orduring addition to a temperature of, for example, from about 0° C. toabout 10° C., for example, from about 0° C. to about 5° C. or from about2° C. to about 3° C. The addition can be conveniently carried out atatmospheric pressure (i.e., about 760 Torr).

iii. Time

In one aspect, the reaction is allowed to stir for a period from about30 minutes to about 6 hours, for example, from about 1 hour to about 4hours, or about 3 hours. One of ordinary skill in the art can readilydetermine completion of the reactions by monitoring consumption ofstarting materials (e.g., alkoxysilyl compound) by chromatographicmethods (e.g., thin layer chromatography (TLC), high performance liquidchromatography (HPLC), or gas chromatography (GC)).

iv. Purification

Upon completion of the reaction, the product can be isolated by removalof the organic layer (i.e., organic solvent and components solubletherein) and disposal of the aqueous layer. The organic layer istypically washed one or more times with brine and then dried overanhydrous sodium sulfate. The crude product can then be filtered,concentrated, and purified by column chromatography (silica gel;hexane/ethyl acetate).

g. Hydrolysis-Resistant Silicone Compound Produced Thereby

Also disclosed are the products produced by the processes of theinvention. In one aspect, the hydrolysis-resistant silicone compoundproduced by the process can have the structure:

wherein M represents a radical-polymerizable group; wherein L representsan optionally substituted divalent C₁-C₂₀ organic group; wherein Z¹ toZ¹¹ independently represent optionally substituted C₁-C₂₀ alkyl groupsor optionally substituted C₆-C₂₀ aryl groups, with the provisos that: atleast one of Z³, Z⁴, and Z⁹ is methyl, and at least one of Z³, Z⁴, andZ⁹ is an organic group having at least two carbon atoms, at least one ofZ⁵, Z⁶, and Z¹⁰ is methyl, and at least one of Z⁵, Z⁶, and Z¹⁰ is anorganic group having at least two carbon atoms, and at least one of Z⁷,Z⁸, and Z¹¹ is methyl, and at least one of Z⁵, Z⁶, and Z¹⁰ is an organicgroup having at least two carbon atoms; wherein n represents an integerof from 0 to 200; and wherein a, b, and c independently representintegers of from 0 to 20, with the proviso that a, b, and c are notsimultaneously 0, as disclosed herein.

In various further aspects, the hydrolysis-resistant silicone compoundcan have the structure:

2. Reaction of Silyl Halide with a Silanol

In one aspect, the invention relates to a process for making a siliconecompound having the structure:

wherein M represents a radical-polymerizable group; wherein L representsan optionally substituted divalent C₁-C₂₀ organic group; wherein R, R¹,R², and R³ independently represent optionally substituted C₁-C₂₀ alkylgroups or optionally substituted C₆-C₂₀ aryl groups, with the provisothat at least one of R¹, R², and R³ is a group having at least 2 carbonatoms; and wherein n represents an integer of from 1 to 3, the processcomprising the step of reacting a silyl halide having the structure:

wherein X represents a halogen selected from the group consisting ofchlorine, bromine, and iodine, with a silanol having the structure:

In a further aspect, water is substantially absent.

a. Radical-Polymerizable Groups

In one aspect, the processes of the invention produce compounds bearingat least one radical-polymerizable group, M. In one aspect, M is anymoiety known to those of skill in the art that can undergo additionpolymerization when exposed to a radical source, for example a radicalinitiator. In a further aspect, M can be an olefin. For example, M canbe an alkene group, including an ethylene, a 1,3-butadiene moiety, or astyryl moiety. In a further aspect, M can be an acrylate. For example, Mcan be a residue of acrylic acid or a derivative thereof (e.g., alkylacrylates) or residue of methacrylic acid or a derivative thereof (e.g.,alkyl methacrylates). Specifically, in one aspect, M can be an acryloylgroup or a methacryloyl group.

It is understood that a one radical-polymerizable group can undergo apolymerization reaction with other radical-polymerizable groups of othercompounds of the invention or with radical-polymerizable groups ofcomonomers, thereby producing a polymer comprising a residue of acompound of the invention.

b. Linking Groups

In one aspect, the processes of the invention produce compounds bearingat least one linking group, L. In one aspect, L can be an optionallysubstituted divalent C₁-C₂₀ organic group, for example, a substituted orunsubstituted C₁-C₁₆ organic group, C₁-C₁₂ organic group, C₁-C₈ organicgroup, or a C₁-C₄ organic group. In a further aspect, linking group, L,can be a substituted or unsubstituted polyalkylene group. That is, L canbe a group having two or more CH₂ groups linked to one another,represented by the formula —(CH₂)_(a)—, where “a” is an integer of from1 to 20. Examples include methylene, ethylene, propylene, butylene,pentylene, and hexylene. The organic group can be branched or linear.

In a further aspect, L has the structure:

wherein k represents an integer of from 0 to 6; and wherein m representsan integer of from 1 to 3 when k is 0, and represents an integer of from1 to 20 when k is not 0, with the proviso that 1≦3k+m≦20.

In a further aspect, k is 1, and wherein m is from 1 to 7. In a yetfurther aspect, k is 0, and m is from 1 to 3. In a still further aspect,L is absent from the processes of the invention.

c. Silyl Halide Compound

In one aspect, the processes of the invention relate to a silyl halidehaving the structure:

In one aspect, X represents a halogen selected from the group consistingof chlorine, bromine, and iodine.

In a further aspect, 3-n is an integer of from 0 to 2. That is, nrepresents an integer of from 1 to 3. For example, n can be 1, 2, or 3,while 3-n can be 2, 1, or 0.

In a yet further aspect, R represents an optionally substituted C₁-C₂₀alkyl group or an optionally substituted C₆-C₂₀ aryl group. The C₁-C₂₀alkyl group can be, for example, a C₁-C₁₆ alkyl group, a C₁-C₁₂ alkylgroup, a C₁-C₈ alkyl group, a C₁-C₆ alkyl group, or aC₁-C₄ alkyl group.Examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl,i-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, neopentyl, hexyl,heptyl, octyl, decyl, and dodecyl. The alkyl group can be branched orlinear. The C₆-C₂₀ aryl group can be, for example, a C₆-C₂₀ aryl group,a C₆-C₁₂ aryl group, or a C₆-C₁₀ aryl group. Examples include phenyl,toluenyl, pyridinyl, and naphthalenyl.

d. Silanol

In one aspect, the processes of the invention relate to a silanol havingthe structure:

In a further aspect, n represents an integer of from 1 to 3. Forexample, n can be 1, 2, or 3.

In a yet further aspect, R¹, R², and R³ independently representoptionally substituted C₁-C₂₀ alkyl groups or optionally substitutedC₆-C₂₀ aryl groups. The C₁-C₂₀ alkyl groups can be, for example, C₁-C₁₆alkyl groups, C₁-C₁₂ alkyl groups, C₁-C₈ alkyl groups, C₁-C₆ alkylgroups, or C₁-C₄ alkyl groups. Examples include methyl, ethyl, n-propyl,i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl,s-pentyl, neopentyl, hexyl, heptyl, octyl, decyl, and dodecyl. The alkylgroups can be branched or linear. The C₆-C₂₀ aryl groups can be, forexample, C₆-C₂₀ aryl groups, C₆-C₁₂ aryl groups, or C₆-C₁₀ aryl groups.Examples include phenyl, toluenyl, pyridinyl, and naphthalenyl.

In a still further aspect, the silanol bears a sterically hinderedterminal silicon group. That is, in one aspect, at least one of R¹, R²,and R³ is a group having at least 2 carbon atoms. That is, one or two orthree of R¹, R², and R³ can be a group having at least 2 carbon atoms,for example, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a decyl group, adodecyl group, a phenyl group, a toluenyl group, pyridinyl group, or anaphthalenyl group. In a yet further aspect, one of R¹, R², and R³ ismethyl, and at least one of R¹, R², and R³ is ethyl, propyl, or butyl.In a still further aspect, two of R¹, R², and R³ are methyl, and one ofR¹, R², and R³ is ethyl, propyl, or butyl.

e. Reaction Conditions

Typically, a silyl halide (e.g., trihalosilane) and at least one molarequivalents of a silanol (e.g., trialkylsilyl alcohol) are added to amixture of an organic solvent and an amine solvent. Thetrialkoxysilylalkylacrylate and the trialkylsilyl halide are typicallyadded separately and are typically added by way of dropping funnels.Such addition is typically performed while the mixture is agitated by,for example, stirring, shaking, or sonicating.

i. Reagents

In one aspect, a silyl halide as disclosed herein, for example atrihalosilane, can be used in connection with the disclosed methods.Typically, one molar equivalent of this reagent is used.

In one aspect, a silanol as disclosed herein, for example atrialkylsilyl alcohol, can be used in connection with the disclosedmethods. Although one of ordinary skill in the art of organic synthesiscan readily determine the relative amount of silanol to be used in areaction, typically, at least one molar equivalent of the silanol,relative to the silyl halide, is used when the silyl halide is amonohalide. Typically, at least two molar equivalents of the silanol,relative to the silyl halide, are used when the silyl halide is adihalide. Typically, at least three molar equivalents of the silanol,relative to the silyl halide, are used when the silyl halide is atrihalide. In a further aspect, when an excess is desired, four, five,six, or more molar equivalents can be used.

In one aspect, an organic solvent can be used in connection with thedisclosed methods. In various aspects, the organic solvent can be anaromatic solvent, including benzene, toluene, naphthalene, ethylbenzene,pyridine, and dimethylaniline; a hydrocarbon, including pentane,cyclopentane, hexane, cyclohexane, heptane, octane, nonane, or decane;an ether, including diethyl ether; or an amide, includingdimethylformamide, dimethylformamide, dimethylacetamide, anddiethylacetamide. Typically, about 3.2 mL of organic solvent is used per1 mmol of silyl halide; however, from about 2.0 mL to about 10.0 mL oforganic solvent can be used per 1 mmol of silyl halide.

In one aspect, an amine solvent can be used in connection with thedisclosed methods. Typically, the amine solvent is an aprotic amine, forexample, and aromatic amine or a tertiary amine. Suitable amine solventsinclude pyridine, N-methylpiperidine, N-methylpyrrolidine,trimethylamine, triethylamine, and dimethylaniline. Typically, about 1mmol of amine solvent is used per 1 mmol of silanol; however, from about1 mmol to about 3.0 mmol of amine solvent can be used per 1 mmol ofsilanol.

ii. Temperature and Pressure

The addition can be conveniently carried out at room temperature (i.e.,about 25° C.). The addition can be conveniently carried out atatmospheric pressure (i.e., about 760 Torr). In a further aspect, thereaction is heated before and/or during addition to a temperature of,for example, from about 25° C. to about 100° C., for example, from about25° C. to about 50° C., from about 50° C. to about 75° C., or from about75° C. to about 100° C. In a further aspect, the reaction is cooledbefore and/or during addition to a temperature of, for example, fromabout 0° C. to about 25° C., for example, from about 0° C. to about 5°C., from about 5° C. to about 10° C., from about 15° C. to about 20° C.,or from about 20° C. to about 25° C.

iii. Time

In one aspect, the reaction is allowed to stir for a period from about30 minutes to about 6 hours, for example, from about 1 hour to about 4hours, or about 3 hours. One of ordinary skill in the art can readilydetermine completion of the reactions by monitoring consumption ofstarting materials (e.g., silyl halide) by chromatographic methods(e.g., thin layer chromatography (TLC), high performance liquidchromatography (HPLC), or gas chromatography (GC)).

iv. Purification

Upon completion of the reaction, the product solution is typicallywashed one or more times with water and then dried over anhydrous sodiumsulfate. The crude product can then be filtered, concentrated, andpurified by column chromatography (silica gel; hexane/ethyl acetate).The product can then be analyzed by, for example, GC to determine theratio of the peak area of the silicone compound of interest to that ofany by-product disiloxane.

f. Hydrolysis-Resistant Silicone Compound Produced Thereby

Also disclosed are the products produced by the processes of theinvention. In one aspect, the hydrolysis-resistant silicone compoundproduced by the process can have the structure:

wherein M represents a radical-polymerizable group; wherein L representsan optionally substituted divalent C₁-C₂₀ organic group; wherein R, R¹,R², and R³ independently represent optionally substituted C₁-C₂₀ alkylgroups or optionally substituted C₆-C₂₀ aryl groups, with the provisothat at least one of R¹, R², and R³ is a group having at least 2 carbonatoms; and wherein n represents an integer of from 1 to 3, as disclosedherein.

3. Yield and Purity

In a further aspect, the processes of the invention can produce acompound having improved yield and/or purity as compared to conventionalprocesses.

a. Improved Yield

The processes of the invention typically exhibit a greater yield thanconventional processes. For example, in one aspect, the inventionrelates to a process for making a silicone compound having thestructure:

as disclosed herein, wherein the silicone compound is produced in ayield of at least about 10% by gas chromatography analysis. For example,the silicone compound can be produced in a yield of at least about 15%,at least about 20%, at least about 25%, at least about 30%, at leastabout 35%, at least about 40%, at least about 45%, or at least about 50%by gas chromatography analysis. In one aspect, water is substantiallyabsent.

The yield of a process can be measured by, for example, gaschromatography (GC) analysis of the obtained crude products, asdescribed in Example 5-1 and Comparative Example 5-1, infra. Comparisonof the peak area attributable to the compound of the invention or theproduct of a process of the invention to the peak area attributable toside products, or to the total areas of all peaks in the chromatogram,can provide a measure of yield.

b. Improved Purity

In one aspect, a disiloxane compound having the structure:

is present in an amount of from about 0% to about 20% by gaschromatography analysis. For example, a disiloxane can be present in anamount of from about 0% to about 15%, from about 0% to about 10%, fromabout 0% to about 5%, from about 0% to about 3%, from about 0% to about3%, from about 0% to about 1%, or about 0% by gas chromatographyanalysis. In one aspect, a disiloxane compound is substantially absent.

Without wishing to be bound by theory, it is believed that the reactionof a silanol (or silanol precursor) with a sterically hindered silylhalide can result in an unsatisfactory amount of undesired disiloxaneside-product. In contrast, again without wishing to be bound by theory,it is believed that the reaction of a sterically hindered silanol with asilyl halide can facilitate the production of desiredhydrolysis-resistant silicone compounds, while minimizing the productionof undesired disiloxane side-product.

D. CYCLIC SILOXANE MONOMERS

In a further aspect, the invention relates to cyclic siloxane monomers,polymers comprising residues of same, processes for making same,processes for polymerizing same. Silicone hydrogels comprising thepolymer have improved thermal stability as compared to conventionalsilicone hydrogels. The cyclic siloxanes can be used as the sole sourceof silicone in silicone hydrogel-forming formulations, or can be used incombination with non-cyclic sloxanes such as TRIS, mPDMS, SiGMA, andothers.

These monomers behave similarly to analogous non-cyclic analogues withrespect to compatibility in the blends, contribution to oxygenpermeability, and the like. For example, like SiGMA, C4-SiGMA canimprove compatibility of silicone hydrogel forming blends, especiallywhen high molecular weight internal wetting agents such as PVP areincluded in the blends.

1. Hydrolytic Stability in Conventional Silicone Hydrogels

Conventional silicone hydrogels have limited hydrolytic stability. Whenthey are heated in water, it is common to observe an increase in themodulus of these materials. For example, the modulus of Purevision®(Bausch & Lomb) lenses increases from 155 to 576 psi when heated at 95°C. for one week. Under typical accelerated aging models, the useableshelf life of some silicone hydrogel lenses can be shortened by thismodulus increase.

Without wishing to be bound by theory, it is believed that the cause ofthis increase in modulus is hydrolysis of terminal siloxane groups,followed by condensation reactions to form new siloxane bonds and tointroduce new cross-links as shown below:

Further, the introduction of ionic carboxylate groups generally leads tosubstantially greater increase in moduli when heated in water. Theincrease in modulus of Purevision® (Bausch & Lomb) lenses is an exampleof this as they are made with VINAL (N-vinylcarboxy-β-alanine), acarboxylic acid-functional monomer. In one aspect, carboxylate groupscan act as nucleophilic catalysts as shown below:

2. Improved Hydrolytic Stability

Monomers that contain small silicone rings and that do not containterminal siloxane groups, such as trimethylsiloxane, typically condenseto reform rings when siloxane bonds are hydrolytically cleaved, as shownbelow:

In other words, the initial equilibrium favors internal condensation toreform the original cyclic siloxanes. Thus, new few new crosslinks areformed, and reduced modulus increase would be observed. Such monomerscan be, for example, either cyclotetrasiloxanes or cyclopentasiloxanes.

In a cyclotrisiloxane methacrylate used to make a silicone hydrogel, themodulus was found to increase. Without wishing to be bound by theory, itis believed that this is because cyclotrisiloxanes are especially proneto undergo ring opening sue to ring strain. Thus, cyclotetrasiloxanesare even more stable.

3. Compounds

In one aspect, the compounds have the structure:

wherein p is 1, 2, or 3; wherein M represents a radical-polymerizablegroup; wherein L represents an optionally substituted divalent C₁-C₂₀organic group; and wherein R¹, R^(2a), R^(2b), R^(3a), R^(3b), R^(4a),and R^(4b) independently represent optionally substituted C₁-C₂₀ alkylgroups or optionally substituted C₆-C₂₀ aryl groups. In a furtheraspect, R^(2a)═R^(2b), R^(3a)═R^(3b), and R^(4a)═R^(4b).

Examples of preferred monomers are C4-TRIS and C4-SiMAA, shown below.

That is, in one aspect, the compound has the structure:

Also, in a further aspect, the compound has the structure:

In various aspects, R¹, R^(2a), R^(2b), R^(3a), R^(3b), R^(4a), andR^(4b) are methyl.

a. Radical-Polymerizable Groups

In one aspect, the improved purity hydrolysis-resistant siliconecompounds of the invention bear at least one radical-polymerizablegroup, M, as disclosed herein. In a further aspect, M is an acryloylgroup, acryloyloxy group, a methacryloyl group, methacryloyloxy group,acrylamide group, methacrylamide group, N-vinylamide group, or styrylgroup. It is also understood that one radical-polymerizable group canundergo a polymerization reaction with other radical-polymerizablegroups of other compounds of the invention or with radical-polymerizablegroups of comonomers, thereby producing a polymer comprising a residueof a compound of the invention. Also disclosed are polymers comprisingat least one residue of a compound of the disclosed cyclic siloxanemonomers.

In a yet further aspect, the polymerizable group can be substituted witha compound having a functional group that can be chemically converted toa polymerizable group. For example, when allyl glycidyl ether is used,the resulting cyclic siloxane epoxide can be reacted with methacrylicacid to form C4-SiMAA.

b. Linking Groups

In one aspect, the improved purity hydrolysis-resistant siliconecompounds of the invention optionally bear at least one linking group,L, as disclosed herein. In a further aspect, L is a divalent linkinggroup having the structure:—(CH₂)_(q)—wherein q is 1, 3, 4, 5, or 6. In a further aspect, q is 3.

In a further aspect, linking group, L, can be substituted by one or morefunctionalized groups. For example, L can be substituted by hydroxygroups, hydroxyalkyl groups, amino groups, aminoalkyl groups, amidegroups, alkylamide groups, alkoxy groups, alkoxyalkyl groups,alkoxycarbonyl groups, alkoxycabonylalkyl groups or a combination ofthose functionalized groups. In a yet further aspect, L can besubstituted by hydroxy groups or hydroxyalkyl groups. Specifically, inone aspect, L can be substituted by hydroxy groups.

In a further aspect, one or more CH₂ groups of linking group, L, can bereplaced by one or more hetero atoms. For example, one or more CH₂groups of L can be replaced by O, S, N—R^(L), P—R^(L) or a combinationof those hetero atoms, wherein R^(L) is substituted or unsubstitutedC₁-C₂₀ alkyl groups or substituted or unsubstituted C₆-C₂₀ aryl groupsand R^(L) can be substituted by one or more functionalized groups andCH₂ groups of R^(L) can be replaced by one or more hetero atoms. In ayet further aspect, one or more CH₂ groups of L can be replaced by O orN—R^(L).

In a further aspect, L has the structure:

wherein G is hydrogen or a hydrolyzable group; wherein k represents aninteger of 0 to 6; and wherein m represents an integer of 1 to 3 when kis 0, and represents an integer of from 1 to 20 when k is not 0, withthe proviso that 1≦3k+m≦20.

4. Processes for Making

In one aspect, the invention relates to processes for making cyclicsiloxane monomers. That is, in various aspects, disclosed are a processcomprising the step of reacting n dihalosilyl compound with a siloxanyldiol compound and

a. Reacting a Dihalosilyl Compound with a Siloxanyl Diol

In one aspect, the invention relates to a process for making a cyclicsiloxane monomer comprising the step of reacting a dihalosilyl compoundhaving the structure:

wherein M represents a radical-polymerizable group; wherein L representsan optionally substituted divalent C₁-C₂₀ organic group; and wherein R¹represents an optionally substituted C₁-C₂₀ alkyl group or optionallysubstituted C₆-C₂₀ aryl group, with a siloxanyl diol compound having thestructure:

wherein p is 1, 2, or 3; and wherein R^(2a), R^(2b), R^(3a), R^(3b),R^(4a), and R^(4b) independently represent optionally substituted C₁-C₂₀alkyl groups or optionally substituted C₆-C₂₀ aryl groups.

In a further aspect, the step can be represented by the followingreaction:

In a further aspect, the cyclic siloxane monomer has the structure:

In a further aspect, the process further comprises the step ofpolymerizing the monomer.

Also disclosed are the product(s) of the process.

b. Hydrosilylating a Unsaturated Compound with a Cyclic Siloxanyl SilaneCompound

In one aspect, the invention relates to a process for making a cyclicsiloxane monomer comprising the step of hydrosilylating a unsaturatedcompound having the structure:

wherein M represents a radical-polymerizable group; wherein L representsan optionally substituted divalent C₁-C₂₀ organic group; and with acyclic siloxanyl silane compound having the structure:

wherein p is 1, 2, or 3; and wherein R¹, R^(2a), R^(2b), R^(3a), R^(3b),R^(4a), and R^(4b) independently represent optionally substituted C₁-C₂₀alkyl groups or optionally substituted C₆-C₂₀ aryl groups, in thepresence of a transition metal catalyst. The cyclic siloxane startingmaterial is typically commercially available.

The transition metal can be, for example, palladium or platinum.

In a further aspect, the step can be represented by the followingreaction:

In a further aspect, the cyclic siloxane monomer has the structure:

In a further aspect, the process further comprises the step ofpolymerizing the monomer.

Also disclosed are the product(s) of the process.

E. HYDROLYSIS-RESISTANT POLYMERS

In one aspect, the invention relates to a polymer comprising at leastone residue of a compound of the invention or at least one residue of aproduct prepared by a process of the invention. That is, one or moresubunits of a hydrolysis-resistant polymer comprise residues of ahydrolysis-resistant compound.

1. Copolymerization

In a further aspect, the polymer compositions of the invention can beprovided as a copolymer. That is, the polymer comprises residues of ahydrolysis-resistant compound and residues of one or more additionalmonomers. For example, the compounds of the invention can becopolymerized with at least one comonomer, for example, a hydrophiliccomonomer. Suitable hydrophilic comonomers include 2-hydroxyethylmethacrylate.

As the polymerizable materials which may be used for thecopolymerization, monomers having a polymerizable carbon-carbonunsaturated bond such as (meth)acryloyl group, styryl group, allylgroup, or vinyl group may be employed.

Preferred examples of such monomers include alkyl (meth)acrylates suchas (meth)acrylic acid, itaconic acid, crotonic acid, cinnamic acid,vinylbenzoic acid, methyl (meth)acrylate and ethyl (meth)acrylate;polyfunctional (meth)acrylates such as polyalkylene glycolmono(meth)acrylate, polyalkylene glycol monoalkyl ether (meth)acrylate,polyalkylene glycol bis(meth)acrylate, trimethylolpropanetris(meth)acrylate, pentaerythritol tetrakis(meth)acrylate, polydimethylsiloxane having (meth)acryloxypropyl group at both ends, polydimethylsiloxane having (meth)acryloxypropyl group at one end and polydimethylsiloxane having a plurality of (meth)acryloyl groups in side chains;halogenated alkyl (meth)acrylates such as trifluoroethyl (meth)acrylateand hexafluoroisopropyl (meth)acrylate; hydroxyalkyl (meth)acrylateshaving hydroxyl group such as 2-hydroxyethyl (meth)acrylate and2,3-dihydroxypropyl (meth)acrylate; (meth)acrylamides such asN,N-dimethylacrylamide, N,N-diethylacrylamide,N,N-di-n-propylacrylamide, N,N-diisopropylacrylamide,N,N-di-n-butylacrylamide, N-acryloylmorpholine, N-acryloylpiperidine,N-acryloylpyrrolidine and N-methyl(meth)acrylamide; N-vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, N-vinylformamide, aromatic vinyl monomers such as styrene, a-methylstyrene andvinylpyridine; maleimides; heterocyclic vinyl monomers such asN-vinylpyrrolidone; 3-[tris(trimethylsiloxy)silyl]propyl (meth)acrylate,3-[bis(trimethylsiloxy)methylsilyl]propyl (meth)acrylate,3-[(trimethylsiloxy)dimethylsilyl]propyl (meth)acrylate,3-[tris(trimethylsiloxy)silyl]propyl (meth)acrylamide,3-[bis(trimethylsiloxy)methylsilyl]propyl (meth)acrylamide,3-[(trimethylsiloxy)dimethylsilyl]propyl (meth)acrylamide,[tris(trimethylsiloxy)silyl]methyl (meth)acrylate,[bis(trimethylsiloxy)methylsilyl]methyl (meth)acrylate,[(trimethylsiloxy)dimethylsilyl]methyl (meth)acrylate,[tris(trimethylsiloxy) silyl]methyl (meth)acrylamide,[bis(trimethylsiloxy)methylsilyl]methyl (meth)acrylamide,[(trimethylsiloxy)dimethylsilyl]methyl (meth)acrylamide,[tris(trimethylsiloxy)silyl]styrene,[bis(trimethylsiloxy)methylsilyl]styrene,[(trimethylsiloxy)dimethylsilyl]styrene, and polydimethyl siloxanehaving (meth)acryloxypropyl group at one end.

Further preferred examples of such monomers include 2-propenoic acid,2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propoxy]propylester (SiGMA); monomethacryloxypropyl-terminated mono-n-butyl terminatedpolydimethylsiloxane (mPDMS; MW 800-1000 (M_(n)));bis-3-acryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane (acPDMS)(MW 1000 and 2000, acrylated polydimethylsiloxane from Gelest andDegussa, respectively); methacryloxypropyl-terminatedpolydimethylsiloxane (MW 550-700) from Gelest (maPDMS); andmono-(3-methacryloxy-2-hydroxypropyloxy)propyl terminated, mono-butylterminated polydimethylsiloxane (mPDMS-OH).

Other silicone containing components suitable for use in this inventioninclude those described in WO 96/31792 such as macromers containingpolysiloxane, polyalkylene ether, diisocyanate, polyfluorinatedhydrocarbon, polyfluorinated ether and polysaccharide groups. U.S. Pat.Nos. 5,321,108; 5,387,662; and 5,539,016 describe polysiloxanes with apolar fluorinated graft or side group having a hydrogen atom attached toa terminal difluoro-substituted carbon atom. US 2002/0016383 describeshydrophilic siloxanyl methacrylates containing ether and siloxanyllinkages and crosslinkable monomers containing polyether andpolysiloxanyl groups.

2. Polymer Makeup

In one aspect, the polymer is a homopolymer. That is, substantially allof the monomer residues comprise residues of a hydrolysis-resistantcompound.

In a further aspect, less than all of the monomer residues compriseresidues of a hydrolysis-resistant compound. In a yet further aspect, atleast 5% of the polymer comprises residues of a compound of theinvention or residues of a product prepared by a process of theinvention. For example, at least 10%, at least 15%, at least 20%, atleast 25%, at least 30%, at least 35%, at least 40%, at least 45%, or atleast 50% of the polymer can comprise residues of a compound of theinvention or residues of a product prepared by a process of theinvention.

In a further aspect, less than all of the mass of the polymer isprovided by residues of a hydrolysis-resistant compound. In a yetfurther aspect, at least 5% of the mass of the polymer is provided byresidues of a compound of the invention or residues of a productprepared by a process of the invention. For example, at least 10%, atleast 15%, at least 20%, at least 25%, at least 30%, at least 35%, atleast 40%, at least 45%, or at least 50% of the mass of the polymer cancomprise residues of a compound of the invention or residues of aproduct prepared by a process of the invention.

F. HYDROLYSIS-RESISTANT COMPOSITIONS

While it is understood that the compounds of the invention and theproducts prepared by a process of the invention can be employed in anyapplication known to those of skill in the art that is suitable forhydrolysis resistant compounds and/or compositions, the compounds,compositions, and products of processes of the invention can be employedas materials for the production of ophthalmic lenses, for example,contact lenses.

In one aspect, the invention relates to an ophthalmic lens comprising apolymer comprising at least one residue of a compound of the inventionor a residue of a product of a process of the invention. In a furtheraspect, the invention relates to an contact lens comprising a polymercomprising at least one residue of a compound of the invention or aresidue of a product of a process of the invention.

G. RESISTANCE TO HYDROLYSIS

Without wishing to be bound by theory, it is believed that compoundsbearing sterically hindered terminal silicon groups have a greaterresistance to hydrolysis conditions (e.g., acid hydrolysis) thancompounds lacking sterically hindered terminal silicon groups.

In one aspect, the compounds of the invention, compositions of theinvention, and products of processes of the invention are hydrolysisresistant. That is, compounds of the invention exhibit greaterhydrolysis resistance than conventional compounds (i.e., compoundslacking a sterically hindered terminal silicon group). Also, acomposition of the invention exhibits greater hydrolysis resistance whencomprising a residue of a compound of the invention or a residue of aproduct of a process of the invention as compared to a similarcomposition in the absence of the residue of the compound or the productof a process.

The hydrolysis resistance of a compound or a product of a process can bemeasured by, for example, heating in the presence of alcohol, water, anacid (e.g., a carboxylic acid, such as acetic acid), and optionally, apolymerization inhibitor (e.g., 2,6-di-t-butyl-4-methylphenol). Themixture can be heated at a hydrolysis temperature (e.g., 80° C. or 90°C.) for a hydrolysis time (e.g., 136 hours or 168 hours), and the degreeof decomposition can be determined by gas chromatography (GC) of thecrude product. By comparing the peak area attributable to the compoundor product being tested before subjecting to hydrolysis conditions tothe peak area attributable to the compound or product being tested aftersubjecting to hydrolysis conditions, the proportion (percentage) of thecompound or product being tested that survives hydrolysis conditions canbe determined.

In various aspects, the compounds of the invention, the products ofprocesses of the invention, and, thus, the compositions of the inventionexhibit a hydrolysis resistance (approximately 5% by weight acetic acidin H₂O/2-propanol; 80° C.; 136 hours) of at least about 90%, at leastabout 92%, at least about 94%, at least about 95%, at least about 96%,at least about 97%, or at least about 98%. In contrast, comparativeexamples of conventional non-hydrolysis resistant compounds can exhibita hydrolysis resistance (approximately 5% by weight acetic acid inH₂O/2-propanol; 80° C.; 136 hours) as low as approximately 46%.

In various further aspects, the compounds of the invention, the productsof processes of the invention, and, thus, the compositions of theinvention exhibit a hydrolysis resistance (approximately 5% by weightacetic acid in H₂O/n-butanol; 90° C.; 136 hours) of at least about 90%,at least about 92%, or at least about 94%. In contrast, comparativeexamples of conventional non-hydrolysis resistant compounds typicallyexhibit a hydrolysis resistance (approximately 5% by weight acetic acidin H₂O/n-butanol; 90° C.; 136 hours) of approximately 78%, approximately61%, or even as low as approximately 35%,

H. COMPOSITIONS WITH SIMILAR FUNCTIONS

It is understood that the compositions disclosed herein have certainfunctions. Disclosed herein are certain structural requirements forperforming the disclosed functions, and it is understood that there area variety of structures which can perform the same function which arerelated to the disclosed structures, and that these structures willultimately achieve the same result.

I. PREPARATION OF MOLDED PLASTICS

Molded plastics can be prepared from the material of the presentinvention by polymerizing the material for producing molded plasticsaccording to the present invention alone or with one or more othermaterials.

For preparing the molded plastics, especially ophthalmic lenses, it canbe preferred to use one or more copolymerizable materials having two ormore polymerizable carbon-carbon unsaturated bonds in the moleculebecause good mechanical properties and good resistance to antisepticsolutions and washing solutions can be obtained. The percentage of thepolymerizable material to be copolymerized, having two or morecopolymerizable carbon-carbon unsaturated bonds in the molecule, basedon the total monomers to be copolymerized, is preferably not less thanabout 0.01% by weight, more preferably not less than about 0.05% byweight, still more preferably not less than about 0.1% by weight.

1. Initiators

In the (co)polymerization for preparing the molded plastics, it ispreferred to add a thermal polymerization initiator orphotopolymerization initiator typified by peroxides and azo compoundsfor easily attaining polymerization. In cases where thermalpolymerization is carried out, one having the optimum decompositioncharacteristics at the satisfactory reaction temperature is selected. Ingeneral, azo initiators and peroxide initiators having a 10 hourhalf-life temperature of from about 40° C. to about 120° C. arepreferred. Examples of the photoinitiator include carbonyl compounds,peroxides, azo compounds, sulfur compounds, halogenated compounds andmetal salts. These polymerization initiators can be used individually orin combination. The amount of the polymerization initiator(s) can be upto about 1% by weight based on the polymerization mixture.

2. Solvents

In (co)polymerizing the material for producing molded plastics accordingto the present invention, a polymerization solvent can be used. As thesolvent, various organic and inorganic solvents can be employed.Examples of the solvents include water; alcoholic solvents such asmethyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol,normal butyl alcohol, isobutyl alcohol, tert-butyl alcohol, ethyleneglycol, diethylene glycol, triethylene glycol, tetraethylene glycol andpolyethylene glycol; glycol ether solvents such as methyl cellosolve,ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, propyleneglycol monomethyl ether, diethylene glycol monomethyl ether, triethyleneglycol monomethyl ether, polyethylene glycol monomethyl ether, ethyleneglycol dimethyl ether, diethylene glycol dimethyl ether, triethyleneglycol dimethyl ether and polyethylene glycol dimethyl ether; estersolvents such as ethyl acetate, butyl acetate, amyl acetate, ethyllactate and methyl benzoate; aliphatic hydrocarbon solvents such asnormal hexane, normal heptane and normal octane; alicyclic hydrocarbonsolvents such as cyclohexane and ethylcyclohexane; ketone solvents suchas acetone, methyl ethyl ketone and methyl isobutyl ketone; aromatichydrocarbon solvents such as benzene, toluene and xylene; and petroleumsolvents. These solvents can be used individually or two or more ofthese solvents can be used in combination.

3. Additives

The molded plastics may contain additional components, including, butnot limited to UV absorbers, colorants, coloring agents, wetting agents,slip agents, pharmaceutical and nutraceutical components,compatibilizing components, antimicrobial compounds, release agents,combinations thereof and the like. Any of the foregoing may beincorporated in non-reactive, polymerizable, and/or copolymerized form.

4. Polymerization

As the method of polymerization of the material for producing moldedplastics according to the present invention, and as the method ofmolding the plastics, known methods can be employed. For example, amethod in which the material is once polymerized and molded into theshape of round bar or plate and the resulting round bar or plate is thenprocessed into the satisfactory shape by cutting or the like, moldpolymerization method and spin cast polymerization method can beemployed.

As an example, a process for producing an ophthalmic lens bypolymerizing the material composition containing the material forproducing molded plastics according to the present invention by moldpolymerization method will now be described.

First, a gap having a prescribed shape, between two mold parts is filledwith the material composition and photopolymerization or thermalpolymerization is carried out to shape the composition into the shape ofthe gap between the molds. The molds are made of a resin, glass,ceramics, metal, or the like. In case of photopolymerization, anoptically transparent material is used, and a resin or glass is usuallyused. In case of producing an ophthalmic lens, a gap is formed betweentwo mold parts facing each other, and the gap is filled with thematerial composition. Depending on the shape of the gap and on theproperties of the material composition, a gasket may be used in order togive the ophthalmic lens a prescribed thickness and to prevent leakageof the material composition filled in the gap. The molds containing thegap filled with the material composition are then irradiated with anactinic radiation such as ultraviolet light, visible light or acombination thereof, or placed in an oven or bath to heat the materialcomposition, thereby carrying out polymerization. The two polymerizationmethods may be employed in combination, that is, thermal polymerizationmay be carried out after photopolymerization, or photopolymerization maybe carried out after thermal polymerization. In photopolymerizationembodiment, a light containing ultraviolet light, such as the light froma mercury lamp or insect lamp is radiated for a short time (usually notlonger than 1 hour). In cases where thermal polymerization is carriedout, it is preferred to employ conditions in which the composition isslowly heated from room temperature to a temperature from about 60° C.to about 200° C. over a period of several hours to several tens hours,in view of the optical uniformity, high quality, and highreproducibility of the ophthalmic lens.

The molded plastics produced from the material of the present inventionmay preferably have a dynamic contact angle (during forward movement,immersion rate: about 0.1 mm/sec) of not more than about 130°, morepreferably not more than about 120°, still more preferably not more thanabout 100°. The water content thereof is preferably from about 3% toabout 0%, more preferably from about 5% to about 50%, still morepreferably from about 7% to about 50%. From the viewpoint of the smallburden to the wearer when the ophthalmic lens is used as a contact lens,the higher the oxygen permeability, the better. The oxygen permeabilitycoefficient [×10⁻¹¹ (cm²/sec)mLO₂/(mL·hPa)] is preferably not less thanabout 50, more preferably not less than about 60, still more preferablynot less than about 65. The tensile modulus of elasticity is preferablyfrom about 0.01 to about 30 MPa, more preferably from about 0.1 to about7 MPa. The tensile elongation is preferably not less than about 50%,more preferably not less than about 100%. Since a higher tensileelongation gives higher resistance to breakage, it is preferred that themolded plastics have a high tensile elongation.

5. Illustrative Uses

In one aspect, the compounds of the invention, compositions of theinvention, and products of processes of the invention provide materialsfrom which molded plastics having enhanced hydrolysis resistance can beproduced. The molded plastics can be useful as drug adsorbents used fordrug delivery and ophthalmic lenses such as contact lenses, intraocularlenses, artificial cornea and spectacle lenses. Among these, they areparticularly suited for contact lenses.

In one aspect, the compounds and compositions of the invention can beused to provide a molded article comprising at least one of thecompositions of the invention. In a further aspect, the compounds andcompositions of the invention can be used to provide an ophthalmic lenscomprising at least one of the compositions of the invention. In a yetfurther aspect, the compounds and compositions of the invention can beused to provide a contact lens comprising at least one of thecompositions of the invention.

J. EXPERIMENTAL

The following examples are put forth so as to provide those of ordinaryskill in the art with a complete disclosure and description of how thecompounds, compositions, articles, devices and/or methods claimed hereinare made and evaluated, and are intended to be purely exemplary of theinvention and are not intended to limit the scope of what the inventorsregard as their invention. Efforts have been made to ensure accuracywith respect to numbers (e.g., amounts, temperature, etc.), but someerrors and deviations should be accounted for. Unless indicatedotherwise, parts are parts by weight, temperature is in ° C. or is atambient temperature, and pressure is at or near atmospheric.

1. Analytical Methodology

a. Gas Chromatography

In the gas chromatographic (GC) analysis, the identification of thepeaks of the siloxanyl compounds represented by the Formula (A1)(wherein n is 0 to 12) is carried out by a separate gas chromatographymass spectrometry (GC-MS).

i. Apparatus and Parameters

Apparatus: Model GC6890 manufactured by HEWLETT-PACKARD or equivalentthereof. Detector: hydrogen flame ionization detector (FID). Column:Restek DB-1HT (30 m×0.25 mm×0.1 μm or equivalent). Carrier Gas: helium.Constant Flow: 1.0 mL/min. Amount of Applied Sample: 2.0 μL. SplitRatio: 30:1. Inlet Temperature: 300° C. Detector Temperature: 350° C.Solvent for Washing Autosampler: 2-propanol. Inlet Septum: Alltech 7/16″HT-X-11 or equivalent thereof

ii. Temperature Program

Initial Temperature: 100° C. Initial time: 2 min. Ramp: 15° C./min;Final Temp: 200° C.; hold for 0 min. Ramp: 5° C./min; Final Temp: 350°C.; hold for 0 min. Ramp: 15° C./min; Final Temp: 400° C.; hold for 15min.

iii. Data Analysis Conditions

Slope Sensitivity: 50. Peak Width: 0.04. Area Reject: 1. HeightReject: 1. Integration Off: from 0 to 4 min.

iv. Preparation of Sample

About 50 μL of a sample is dissolved in 1.0 mL of 2-propanol. The sampleand 2-propanol are directly placed in a vial for GC and mixed therein.

b. Gas Chromatography-Mass Spectrometry

Gas chromatography-mass spectrometry (GC-MS) analysis was carried out bycarrying out the GC analysis under the conditions described above in thesection <GC Analysis Conditions>, and by using as a mass spectrometerJMS-DX303 manufactured by JEOL.

c. Gel Permeation Chromatography

GPC was performed under the following conditions: Column: Shodex GPCK-801 and Shodex GPC K-802 manufactured by SHOKO CO., LTD. (each of themhas an inner diameter of 8.0 mm and a length of 30 cm). The two columnswere connected in series. Solvent: chloroform. Column Temperature: 40°C. Flow Rate: 1.0 mL/min. Apparatus: HLC-8022GPC manufactured by TOSOHCORPORATION, which is an integral apparatus combining a UV detector anda differential refractometer.

d. Matrix-Assisted Laser Desorption/Ionisation Time-of-Flight MassSpectrometry

For matrix-assisted laser desorption/ionisation time-of-flight massspectrometry (MALDI-TOF MS), AXIMA-CFR plus manufactured by SHIMADZUCORPORATION was used.

e. Oxygen Permeability Coefficient Testing

A sample's oxygen permeability coefficient was determined by using aSeikaken-shiki film oxygen permeability meter manufactured by RIKA SEIKIKOGYO CO., LTD. The oxygen permeability coefficient of a sample in theform of a film was measured in water at 35° C. Four film samples withdifferent thickness were prepared (0.1 mm, 0.2 mm, 0.3 mm, and 0.4 mm;diameter 16 mm). The four samples with different thickness were measuredto determine Pm of every example (see FIG. 1). One of the samples wasset at an electrode. 0.5 N KCl (aqueous) was poured into the electrodeas an electrolytic solution (see FIGS. 2-4). The electrode was set indistilled water (pH=7, volume=800 ml). At first, the current undernitrogen bubbling (flow rate=100 mL/min.; electric current, i, ismeasured after it is in equilibrium) was measured in order to adjustzero. Then the current under oxygen bubbling was measured. R wascalculated by the following formula: R=(Ps×N×F×A)/i [cm² sec mmHg/mL(STP)] (wherein Ps=760 mmHg (atmospheric pressure), N=4 (the number ofelectrons which involves a reaction at the electrode), F=96500coulomb/mol (Faraday constant), A=area of the electrode (cm²),i=measured current (uA)). R involves constant (not proportional) part,so plural measurement and plotting are necessary to determine Pm (seeFIG. 1). R versus the thickness of the samples was plotted. The inverseof the slope is the oxygen permeability coefficient (Pm).

f. Moisture Content

A sample in the form of a film sizing about 10 mm×10 mm×0.2 mm was used.The sample was dried in a vacuum dryer at 40° C. for 16 hours, and theweight (Wd) of the sample was measured. Thereafter, the resulting samplewas immersed in pure water at 40° C. in a thermostat bath overnight ormore, and the moisture on the surface was wiped with Kimwipe, followedby measurement of the weight (Ww). The moisture content was calculatedaccording to the following equation:Moisture Content(%)=100×(Ww−Wd)/Ww

g. Tensile Modulus of Elasticity

Tensile Test: a sample in the form of a film sizing about 19.5 mm×15mm×0.2 mm was used. The tensile modulus of elasticity was measured usingTensilon type RTM-100 manufactured by ORIENTEC. The speed of pulling was100 mm/min and the distance between grips was 5 mm.

h. Optical Non-Uniformity

A sample molded into the form of contact lens was irradiated with lightwith a projector for photograph films to project its image on a screen,and the projected image on the screen was visually observed to evaluatethe degree of optical non-uniformity. The evaluation was performed byclassification into the following three ranks:

A: Distortion or turbidity is not observed at all.

B: Distortion or turbidity is observed very slightly.

C: Distortion or turbidity is observed.

2. Example 4-1

To a 50-mL eggplant type flask, 5 mL of water, 2.5 mL of methanol and2.5 mL of hexane were added, and the resulting mixture was cooled to 2to 3° C. under stirring on ice, followed by dropping a mixture of 2.48 g(10 mmol) of 3-trimethoxysilylpropyl methacrylate and 7.36 g (60 mmol)of ethyldimethylchlorosilane from a dropping funnel. After the dropping,the reaction solution was stirred at room temperature for 3 hours, andthe disappearance of the starting materials was confirmed by gaschromatography (GC), which was regarded as the completion of thereaction. After completion of the reaction, stirring was stopped and theaqueous layer was discarded. The organic layer was transferred to aseparation funnel, washed once with saturated aqueous sodium hydrogencarbonate solution and twice with saturated saline, and dried overanhydrous sodium sulfate. The resultant was filtered, and the solventwas evaporated with an evaporator. The obtained crude product waspurified by column chromatography on 40 g of silica gel using 80 mL eachof 20/1, 15/1, 10/1, 7/1, 4/1, and 4/1 mixtures of hexane/ethyl acetateas eluents, to obtain the silicone compound represented by the Formula(4p1) below.

3. Example 4-2

The same synthesis and purification operations as in Example 4-1 wererepeated except that n-propyldimethylchlorosilane was used in place ofethyldimethylchlorosilane to obtain the silicone compound represented bythe Formula (4p2) below.

4. Example 4-3

The same synthesis and purification operations as in Example 4-1 wererepeated except that n-butyldimethylchlorosilane was used in place ofethyldimethylchlorosilane to obtain the silicone compound represented bythe Formula (4p3) below.

5. Comparative Example 4-1

The same synthesis and purification operations as in Example 4-1 wererepeated except that triethylchlorosilane was used in place ofethyldimethylchlorosilane to obtain the silicone compound represented bythe Formula (4r1) below.

6. Comparative Example 4-2

The silicone compound represented by the Formula (4r2) below wassynthesized by the method described in Japanese Laid-open PatentApplication (Kokai) No. 56-22325. The obtained liquid was purified bysilica gel column chromatography.

7. Example 4-5 Hydrolysis Resistance Test at 80° C.

The silicone compounds obtained in the above-described Example 4-1,Example 4-2, and Example 4-3 and Comparative Examples 4-1 and 4-2, aswell as a commercially available silicone compound (Comparative Example4-3) represented by the Formula (4r3) below were tested for theirhydrolysis resistance in the presence of a carboxylic acid.

A solution of 0.1 g of the silicone compound, 3.90 g of 2-propanol, 0.24g of acetic acid, 0.90 g of water and 2 mg of2,6-di-t-butyl-4-methylphenol as a polymerization inhibitor wasprepared. The obtained solution was heated in an oven at 80° C. for 168hours, and the degree of decomposition was measured by gaschromatography (GC). Taking the GC area % of the peak of the siliconecompound at the beginning (0 hr) of the test as 100, the ratios of theGC area % of the peak of the respective silicone compounds at 136 hoursfrom the beginning of the test are shown in Table 1 in the columnindicated by the heading “80° C.”.

8. Example 4-6 Hydrolysis Resistance Test at 90° C.

The same test as in Example 4-5 above was repeated except that n-butanolhaving a higher boiling point than 2-propanol was used in place of2-propanol. The results are shown in the column indicated by the heading“90° C.” in Table 1.

TABLE 1 80° C. 90° C. Example 4-1 97 92 Example 4-2 94 90 Example 4-3 9894 Comparative Example 4-1 98 78 Comparative Example 4-2 46 35Comparative Example 4-3 73 61

9. Example 4-7 Preparation of Lens

The silicone compound (30 parts by weight) represented by Formula (p1)obtained in Example 4-1, N,N-dimethylacrylamide (40 parts by weight),polydimethylsiloxane of which terminals are methacrylated (molecularweight: about 1000, 30 parts by weight), triethylene glycoldimethacrylate (1 part by weight), methacrylic acid (1 part by weight)and Darocure 1173 (CIBA, 0.2 parts by weight) were mixed and stirred toobtain a uniform transparent monomer mixture. The monomer mixture wasdegassed under argon atmosphere. This monomer mixture was poured into amold for contact lens, which was made of a transparent resin(poly(4-methylpent-1-ene), in a glove box under nitrogen atmosphere, andthe mold was irradiated with light (1 mW/cm², 10 minutes) with afluorescent lamp (e.g., of the type used for insect control) topolymerize the monomers, thereby obtaining a contact lens-shaped sample.

The obtained lens-shaped sample was subjected to hydration treatment andthen immersed in 5 wt % aqueous polyacrylic acid (molecular weight:about 150,000) solution at 40° C. for 8 hours, thereby modifying thesample. After the modification treatment, the sample was sufficientlywashed with purified water, and immersed in borate buffer (pH of 7.1 to7.3) in a vial container. After sealing, the vial container wasautoclaved for 30 minutes at 120° C. After allowing the vial containerto cool, the lens-shaped sample was taken out from the vial container,and immersed in borate buffer (pH of 7.1 to 7.3). The obtained samplewas transparent and free from turbidity, and suitable for use as acontact lens.

10. Example 5-1

To a 500-mL three-necked flask to which two dropping funnels wereattached, 80 mL of toluene and 11.85 g (75 mmol) of pyridine were added.Under stirring the resulting mixture at the room temperature, a solutionof 6.55 g (25 mmol) of 3-trichlorosilylpropyl methacrylate in 50 mL oftoluene was dropped from a dropping funnel, while simultaneouslydropping 9.90 g (75 mmol) of triethylsilanol from the other droppingfunnel. After the dropping, the reaction solution was stirred at roomtemperature for 3 hours, and the disappearance of the starting materialswas confirmed by gas chromatography (GC), which was regarded as thecompletion of the reaction. The reaction solution was washed with water,dried over anhydrous sodium sulfate, and the organic solvent wasevaporated with an evaporator, thereby obtaining a liquid of a crudeproduct. GC analysis of the obtained liquid revealed that the ratio ofthe peak area of the silicone compound of interest to that of aby-product disiloxane was as shown in Table 2.

The obtained liquid of a crude product was purified by columnchromatography on silica gel in an amount of 40 g per 10 g of theobtained liquid using 80 mL each of 20/1, 15/1, 10/1, 7/1, 4/1, and 4/1mixtures of hexane/ethyl acetate as eluents, to obtain the siliconecompound represented by the Formula (5p1) below.

11. Comparative Example 5-1

To a 50-mL eggplant type flask, 5 mL of water, 2.5 mL of methanol and2.5 mL of hexane were added, and the resulting mixture was cooled to 2to 3° C. under stirring on ice, followed by dropping a mixture of 2.48 g(10 mmol) of 3-trimethoxysilylpropyl methacrylate and 7.36 g (60 mmol)of triethylchlorosilane from a dropping funnel. After the addition wascomplete, the reaction solution was stirred at room temperature for 3hours, and the disappearance of the starting materials was confirmed bygas chromatography (GC), which was regarded as the completion of thereaction. After completion of the reaction, stirring was stopped, andthe aqueous layer was discarded. The organic layer was transferred to aseparation funnel, washed once with saturated aqueous sodium hydrogencarbonate solution and twice with saturated saline, and dried overanhydrous sodium sulfate. The resultant was filtered, and the solventwas evaporated with an evaporator. GC analysis of the obtained crudeproduct revealed the ratio of the peak area of the silicone compound(5p1) to that of a by-product hexaethyldisiloxane was as shown in Table2.

TABLE 2 silicone compound (p1) disiloxane others Example 5-1 67.2 2.730.1 Comparative Example 5-1 1.9 76.3 21.8

12. Comparative Example 5-2

The same reaction procedures as in Comparative Example 5-1 were repeatedexcept that trimethylchlorosilane was used in place oftriethylchlorosilane. GC analysis of the obtained crude product revealedthat 3-tris(trimethylsiloxy)silylpropyl methacrylate was obtained at aratio of 69.8% in terms of GC area % as a major product.

It will be apparent to those skilled in the art that variousmodifications and variations can be made in the present inventionwithout departing from the scope or spirit of the invention. Otherembodiments of the invention will be apparent to those skilled in theart from consideration of the specification and practice of theinvention disclosed herein. It is intended that the specification andexamples be considered as exemplary only, with a true scope and spiritof the invention being indicated by the following claims.

What is claimed is:
 1. A process for making a hydrolysis-resistantsilicone compound having a sterically hindered terminal silicon group,the process comprising the step of reacting an alkoxysilyl compoundhaving the structure:

with one or more silyl halide compounds having the structure:

wherein X¹, X², and X³ independently represent a halogen selected fromthe group consisting of chlorine, bromine, and iodine; wherein Mrepresents a radical-polymerizable group; wherein L represents anoptionally substituted divalent C₁-C₂₀ organic group; wherein nrepresents an integer of from 0 to 200; wherein Q¹, Q², and Q³independently represent hydrogen or a hydrolyzable group; wherein Z¹ toZ¹¹ independently represent optionally substituted C₁-C₂₀ alkyl groupsor optionally substituted C₆-C₂₀ aryl groups, with the provisos that: atleast one of Z³, Z⁴, and Z⁹ is methyl, and at least one is an organicgroup having at least two carbon atoms, at least one of Z⁵, Z⁶, and Z¹⁰is methyl, and at least one is an organic group having at least twocarbon atoms, and at least one of Z⁷, Z⁸, and Z¹¹ is methyl, and atleast one is an organic group having at least two carbon atoms; whereina, a′, b, b′, c, and c′ independently represent integers of from 0 to20; and wherein (a+a′), (b+b′), and (c+c′) are, independently, integersof from 0 to 20, with the proviso that (a+a′), (b+b′), and (c+c′) arenot simultaneously
 0. 2. The process of claim 1, wherein M is anacryloyloxy group, a methacryloyloxy group, acrylamide group,methacrylamide group, N-vinylamide group, or styryl group.
 3. Theprocess of claim 2, wherein M is an acryloyloxy group or amethacryloyloxy group.
 4. The process of claim 1, wherein L has thestructure:

wherein G is hydrogen or a hydrolyzable group; wherein k represents aninteger of 0 to 6; and wherein m represents an integer of 1 to 3 when kis 0, and represents an integer of from 1 to 20 when k is not 0, withthe proviso that 1≦3k+m≦20.
 5. The process of claim 1, wherein Q¹, Q²,and Q³ independently represent alkyl.
 6. The process of claim 1, whereinthe alkoxysilyl compound has the structure:


7. The process of claim 1, wherein the silyl halide compound has thestructure:


8. The process of claim 1, wherein the hydrolysis-resistant siliconecompound has the structure: